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Sample records for chromium carbene complexes

  1. Synthesis and structure of the unligated carbene of chromium

    Energy Technology Data Exchange (ETDEWEB)

    Billups, W.E.; Souchan Chang; Hauge, R.H.; Margrave, J.L. (Rice Univ., Houston, TX (United States))

    1993-04-14

    Complexes with metal-carbon double bonds have found applications as intermediates in many important catalytic reactions including cyclopropanation of alkenes by diazoalkanes, Fischer-Tropsch synthesis, olefin metathesis, Ziegler-Natta polymerization, alkane activation, and in the decomposition of transition metal alkyl complexes. However, complexes with the simplest carbene, CH[sub 2], coordinated to the metal center are relatively rare. In this paper the authors report the synthesis and characterization of the simple unligated carbene of chromium by FTIR matrix isolation spectroscopy. 7 refs., 3 figs., 4 tabs.

  2. Uranium nucleophilic carbene complexes

    International Nuclear Information System (INIS)

    Tourneux, Jean-Christophe

    2012-01-01

    The only stable f-metal carbene complexes (excluding NHC) metals f present R 2 C 2- groups having one or two phosphorus atoms in the central carbon in alpha position. The objective of this work was to develop the chemistry of carbenes for uranium (metal 5f) with the di-anion C{Ph 2 P(=S)} 2 2- (SCS 2- ) to extend the organometallic chemistry of this element in its various oxidation states (+3-+6), and to reveal the influence of the 5f orbitals on the nature and reactivity of the double bond C=U. We first isolated the reactants M(SCHS) (M = Li and K) and demonstrated the role of the cation M + on the evolution of the di-anion M 2 SCS (M = Li, K, Tl) which is transformed into LiSCHS in THF or into product of intramolecular cyclization K 2 [C(PhPS) 2 (C 6 H 4 )]. We have developed the necessary conditions mono-, bis- and tris-carbene directly from the di-anion SCS 2- and UCl 4 , as the precursor used in uranium chemistry. The protonolysis reactions of amides compounds (U-NEt 2 ) by the neutral ligand SCH 2 S were also studied. The compounds [Li(THF)] 2 [U(SCS)Cl 3 ] and [U(SCS)Cl 2 (THF) 2 ] were then used to prepare a variety of cyclopentadienyl and mono-cyclo-octa-tetra-enyliques uranium(IV) carbene compounds of the DFT analysis of compounds [M(SCS)Cl 2 (py) 2 ] and [M(Cp) 2 (SCS)] (M = U, Zr) reveals the strong polarization of the M=C double bond, provides information on the nature of the σ and π interactions in this binding, and shows the important role of f orbitals. The influence of ancillary ligands on the M=C bond is revealed by examining the effects of replacing Cl - ligands and pyridine by C 5 H 5 - groups. Mulliken and NBO analyzes show that U=C bond, unlike the Zr=C bond, is not affected by the change in environment of the metal center. While the oxidation tests of carbene complexes of U(IV) were disappointing, the first carbene complex of uranium (VI), [UO 2 (SCS)(THF) 2 ], was isolated with the uranyl ion UO 2 2+ . The reactions of compounds UO 2 X 2

  3. Electrochemistry of chromium(0)-aminocarbene complexes

    International Nuclear Information System (INIS)

    Hoskovcova, Irena; Rohacova, Jana; Meca, Ludek; Tobrman, Tomas; Dvorak, Dalimil; Ludvik, Jiri

    2005-01-01

    Two series of chromium(0)-(aryl)aminocarbene complexes substituted on the ligand phenyl ring were prepared and electrochemically investigated: pentacarbonyl((N,N-dimethylamino)(phenyl)carbene(chromium(0) (Ia-e) and chelated tetracarbonyl((η 2 -N-allyl-N-allylamino)(phenyl)carbene(chromium(0) (IIa, c-e). For comparison, a tungsten analogue of IIc (III) and a chromium chelate bearing a methyl substituent instead of the phenyl group IV were taken into the study. The intramolecular interactions of p-substituents on the ligand phenyl ring with the reduction and oxidation centres of the molecule of complex (followed electrochemically using LFER [P. Zuman, Substituent Effects in Organic Polarography, Plenum Press, New York, 1967]) enabled to localize the corresponding electron transfer. The influence of the type of coordination, the substituent on the ligand phenyl ring and the central metal atom on oxidation and reduction potentials is discussed

  4. -Heterocyclic Carbene Complexes of Mineral Acids

    KAUST Repository

    Brill, Marcel; Nahra, Fady; Gó mez-Herrera, Alberto; Zinser, Caroline; Cordes, David B.; Slawin, Alexandra M. Z.; Nolan, Steven P.

    2016-01-01

    We have synthesized and characterized new gold-N-heterocyclic carbene (NHC) complexes derived from the deprotonation of mineral acids. The use of sulfuric acid was a particularly interesting case. These complexes were tested in known gold-catalyzed reactions, such as the hydration of alkynes and the Meyer–Schuster rearrangement. They proved to be highly efficient in both reactions.

  5. -Heterocyclic Carbene Complexes of Mineral Acids

    KAUST Repository

    Brill, Marcel

    2016-11-08

    We have synthesized and characterized new gold-N-heterocyclic carbene (NHC) complexes derived from the deprotonation of mineral acids. The use of sulfuric acid was a particularly interesting case. These complexes were tested in known gold-catalyzed reactions, such as the hydration of alkynes and the Meyer–Schuster rearrangement. They proved to be highly efficient in both reactions.

  6. Enyne Metathesis Catalyzed by Ruthenium Carbene Complexes

    DEFF Research Database (Denmark)

    Poulsen, Carina Storm; Madsen, Robert

    2003-01-01

    Enyne metathesis combines an alkene and an alkyne into a 1,3-diene. The first enyne metathesis reaction catalyzed by a ruthenium carbene complex was reported in 1994. This review covers the advances in this transformation during the last eight years with particular emphasis on methodology...

  7. Electron pairing analysis of the Fischer-type chromium-carbene complexes (CO){sub 5}Cr=C(X)R (X=H, OH, OCH{sub 3}, NH{sub 2}, NHCH{sub 3} and R=H, CH{sub 3}, CH=CH{sub 2}, Ph, C-CH )

    Energy Technology Data Exchange (ETDEWEB)

    Poater, Jordi; Cases, Montserrat; Fradera, Xavier; Duran, Miquel; Sola, Miquel

    2003-10-15

    The electron-pair density distributions of a series of 25 Fischer carbene complexes of the type (CO){sub 5}Cr=C(X)R (X=H, OH, OCH{sub 3}, NH{sub 2}, NHCH{sub 3} and R=H, CH{sub 3}, CH=CH{sub 2}, Ph, C-CH) are analyzed using the Atoms in Molecules theory. Localization and delocalization indices are used to characterize the electron pairing taking place in the Cr=C---X moiety in these complexes. Electron delocalization between the Cr and C atoms and between the C atom and the X group are related to the {pi}-donor strength of the X group and the degree of back-donation between the chromium pentacarbonyl and the carbene fragments. The results obtained with the Atoms in Molecules theory complement those obtained in a previous study by means of energy and charge decomposition analyses. Electron delocalization between the Cr atom and the X group is consistent with the hypothesis of a weak 3-center 4-electron bonding interaction in the Cr=C-X group of atoms. Except for X=H, {delta}(Cr,X) increases with the decrease of the {pi}-donor character of the X group.

  8. Rhenium carbene complexes and their applications; Rhenium-Carben-Komplexe und ihre Anwendungen

    Energy Technology Data Exchange (ETDEWEB)

    Hille, Claudia Heidi

    2016-01-25

    New pharmaceutically suitable metal complexes play an important role in the development of diagnostic and therapeutic agents for cancer treatment. One option concerning new radiopharmaceuticals, is the application of the rhenium isotopes {sup 186}Re and {sup 188}Re. Therefore, water soluble but at the same time stable complexes, which can be synthesized straightforward, are required. In this thesis, several synthetic pathways to such rhenium complexes bearing Nheterocyclic carbenes are presented and applicability tests of literature known complexes conducted. The selected target structures based on monocarbenes turned out to be inappropriate for use in radiopharmaceutical applications, due to their long reaction times and purification issues. Additionally, sterical and electronical effects of the carbene ligands concerning complex formation have been investigated. Possibilities of functionalization at different positions on the heterocycle as well as hydrophilic wingtips - to achieve a better stability in an aqueous media - have been examined to gain information about chemical and physical properties of the resulting complexes. Furthermore, experiments regarding the coordination of various biscarbene ligands, which provides besides the stable chelatisation additionally the possibility of varying the linking bridge, to rhenium(I/V) precursors, have been performed. Dioxo-bis-(1,1{sup '}-methylene-bis(3,3{sup '}-diisopropylimidazolium-2-ylidene)) rhenium(V )-hexafluorophosphate was synthesized via a transmetalation reaction of the corresponding silver carbene with ReOCl{sub 3}(PPh{sub 3}){sub 2} and silver hexafluorophosphate. This complex provided the basis for the first radiolabeled {sup 188}Rhenium NHC complex later on. An enhancement of the kinetic and thermodynamic stability of potential rhenium biscarbene complexes based on modifications concerning the length and character of the bridging moiety between the chelating NHC rings as well as the nature of

  9. Synthesis of Backfunctionalized Imidazolinium Salts and NHC Carbene Complexes

    Science.gov (United States)

    2017-04-02

    Backfunctionalized Imidazolinium salts and NHC carbene complexes – Initial Research – Unintended Discovery – Survey chemistry of aromatic systems – Expansion of...survey chemistry to aliphatics • Conclusions and Future Directions Introduction 3 Distribution A: Approved for Public Release; Distribution Unlimited...AFRL – Tenant of Edwards AFB since late ‘50s – Full scale testing of the Atlas rockets (Gemini missions) – Initial testing of the F-1 engine (Apollo

  10. Reactions of Fischer carbene complexes with Electron-deficient olefins: Scope and limitations of this route to donor-acceptor-substituted cyclopropanes

    Energy Technology Data Exchange (ETDEWEB)

    Wienand, A.; Reissig, H.U. (Inst. fuer Organische Chemie der Technischen Hochschule Darmstadt (West Germany))

    1990-12-01

    The Fischer carbene complex ((CO){sub 5}Cr{double bond}C(OMe)Ph) (1) is able to transfer its carbene ligand to a variety of electron-deficient olefins and provides donor-acceptor-substituted cyclopropanes in good yields. Apt activating groups with respect to the alkene are ester, amide, nitrile, sulfone, and dialkyl phosphonate functions. Methyl vinyl ketone (19) affords products in low yield that may arise from an intermediate cyclopropane derivative. Phenyl vinyl sulfoxide (24) mainly acts as an oxidizing agent, transforming 1 into methyl benzoate. for olefin 24 and {alpha}-(N-methylanilino)acrylonitrile the authors found products that should be formed on an olefin metathesis pathway. The methyl-substituted carbene complex 48 also affords the expected donor-acceptor-substituted cyclopropanes; however, acyclic isomers are formed in higher amounts. The molybdenum and tungsten complexes 55 and 56, respectively, also furnish cyclopropane derivatives, but the yields are lower than with the chromium compound 1. Disubstituted olefins and complex 1 still give the cyclopropanes in moderate yields, while all trisubstituted and most of the difunctionalized alkenes do not react with this Fischer carbene complex. The cyclopropanes synthesized can be deprotonated and alkylated or transformed into ring-opened products. These model reactions demonstrate the synthetic potentials of donor-acceptor-substituted cyclopropanes prepared via Fischer carbene complexes.

  11. Formation of quinones, indanones and furans by the reaction of molybdenum carbene complexes with alkynes

    International Nuclear Information System (INIS)

    Doetz, K.H.; Larbig, H.

    1992-01-01

    (Alkoxy)carbene complexes of molybdenum react with terminal alkynes to give carbene annulation of cycloaddition products, the skeleton of which depends on the carbene substitution pattern and the alkyne used. (CO) 5 Mo=C(OMe)-p-tol undergoes carbene annulation upon reaction with trimethylsilylacetylene leading to naphthoquinone after oxidative work-up. Similar products are obtained from (CO) 5 Mo=C(OMe)2-furyl and hex-1-yne or oct-1-yne. The reaction of these alkynes results in the formation of indanones as five-membered annulation products. In the presence of 3.3-dimethylbut-1-yne the (phenyl) carbene ligands act as a C 1 -synthon, which is incorporated into the furan cycloaddition products

  12. Theoretical NMR spectroscopy of N-heterocyclic carbenes and their metal complexes

    KAUST Repository

    Falivene, Laura; Cavallo, Luigi

    2016-01-01

    Recent theoretical analysis of the NMR properties of free N-heterocyclic carbenes (NHC) and Metal-NHC complexes has complemented experiments, allowing the establishment of structure/property relationships and the rationalization of otherwise

  13. {alpha},{beta}-Unsaturated Fischer carbene complexes as chemical multitalents

    Energy Technology Data Exchange (ETDEWEB)

    Meijere, A. de [Institut fuer Organische Chemie der George-August-Universitaet Goettingen (Germany)

    1995-12-31

    The well established reaction of {alpha},{beta}-unsaturated Fischer carbenechromium complexes 6(R{sup 1} = H) with alkynes normally proceeds with carbonyl insertion to yield 4-alkoxyphenols 9. Led by the incidental formation of a cyclopentadiene 3 from certain {beta}-aminosubstituted complexes 6(X = NR{sub 2}{sup 3}, R{sup 1} = cPr) the authors have studied the influences of the nature of substituents (R{sup 1}, X on 6; R{sub L}, R{sub S} in the alkyne; R{sup 3} in the amino group), solvents, and temperature on the outcome of the reaction. Imino substitution on complexes 6 leads to 2H-pyrroles 1, a free primary amino group (X = NH{sub 2}) to pyridines 5, and bulky substituents R{sup 1} to cyclopenta[b]pyrans 8 with double insertion of an alkyne. Eventually, appropriate conditions have been developed which permit to selectively prepare either 3-alkoxy-5-(dialkylamino)cyclopentadienes 3 (as synthetic equivalents of cyclopentenones 4), 5-(dialkylaminomethylene)cyclopent-2-enones 7, 3-alkoxy-2-(1{prime}-morpholino-1{prime}-alkenyl)cyclopent-2-enones 10, and 2-acyl-3-(dialkylamino)cyclopent-2-enones 11 from easily accessible carbene complexes 6 (X = NR{sub 2}{sup 3}) in high yields. Mechanistic aspects and implications of these novel transformations will be discussed.

  14. A simple building-block route to (phosphanyl-carbene)palladium complexes via intermolecular addition of functionalised phosphanes to isocyanides

    NARCIS (Netherlands)

    Eberhard, M.R.; van Vliet, B.; Durán Páchon, L.; Rothenberg, G.; Eastham, G.; Kooijman, H.; Spek, A.L.; Elsevier, C.J.

    2009-01-01

    We present a straightforward protocol for making (phosphanyl-carbene)PdII complexes. These complexes have bidentate ligands containing an acyclic diamino- or aminooxy-carbene and a phosphane. The synthesis gives good yields (typically 70-90 %) for a variety of complexes (22 compounds). Moreover, it

  15. Synthesis and Properties of Chelating N-Heterocyclic Carbene Rhodium(I) Complexes: Synthetic Experiments in Current Organometallic Chemistry

    Science.gov (United States)

    Mata, Jose A.; Poyatos, Macarena; Mas-Marza, Elena

    2011-01-01

    The preparation and characterization of two air-stable Rh(I) complexes bearing a chelating N-heterocyclic carbene (NHC) ligand is described. The synthesis involves the preparation of a Ag(I)-NHC complex and its use as carbene transfer agent to a Rh(I) precursor. The so obtained complex can be further reacted with carbon monoxide to give the…

  16. N-heterocyclic carbene complexes of silver and gold as novel tools against breast cancer progression.

    Science.gov (United States)

    Saturnino, Carmela; Barone, Ines; Iacopetta, Domenico; Mariconda, Annaluisa; Sinicropi, Maria Stefania; Rosano, Camillo; Campana, Antonella; Catalano, Stefania; Longo, Pasquale; Andò, Sebastiano

    2016-12-01

    Metal carbenic complexes have received considerable attention in both the catalysis and biological fields for their potential applications in cancer and antimicrobial therapies. A small series of new silver and gold N-heterocyclic carbene complexes has been designed and synthesized. Among the tested complexes, one compound was particularly active in inhibiting anchorage-dependent and -independent breast cancer proliferation, and inducing cell apoptosis via a mitochondria-related process. The antitumor activity was associated to the transcriptional activation of the tumor suppressor gene p53 in an Sp1-dependent manner, as evidenced by biological and docking studies. Our results highlight the importance and the versatility of N-heterocyclic carbene complexes of gold and silver as useful tools against breast cancer progression.

  17. Synthesis, characterization, and reactivity of a uranium(VI) carbene imido oxo complex

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Erli; Cooper, Oliver J.; McMaster, Jonathan; Lewis, William; Blake, Alexander J.; Liddle, Stephen T. [Nottingham Univ. (United Kingdom). School of Chemistry; Tuna, Floriana; McInnes, Eric J.L. [Manchester Univ. (United Kingdom). School of Chemistry and Photon Science Inst.

    2014-06-23

    We report the uranium(VI) carbene imido oxo complex [U(BIPM{sup TMS})(NMes)(O)(DMAP){sub 2}] (5, BIPM{sup TMS}=C(PPh{sub 2}NSiMe{sub 3}){sub 2}; Mes=2,4,6-Me{sub 3}C{sub 6}H{sub 2}; DMAP=4-(dimethylamino)pyridine) which exhibits the unprecedented arrangement of three formal multiply bonded ligands to one metal center where the coordinated heteroatoms derive from different element groups. This complex was prepared by incorporation of carbene, imido, and then oxo groups at the uranium center by salt elimination, protonolysis, and two-electron oxidation, respectively. The oxo and imido groups adopt axial positions in a T-shaped motif with respect to the carbene, which is consistent with an inverse trans-influence. Complex 5 reacts with tert-butylisocyanate at the imido rather than carbene group to afford the uranyl(VI) carbene complex [U(BIPM{sup TMS})(O){sub 2}(DMAP){sub 2}] (6).

  18. Synthesis, characterization, and reactivity of a uranium(VI) carbene imido oxo complex

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Erli; Cooper, Oliver J.; McMaster, Jonathan; Lewis, William; Blake, Alexander J.; Liddle, Stephen T. [School of Chemistry, University of Nottingham (United Kingdom); Tuna, Floriana; McInnes, Eric J.L. [School of Chemistry and Photon Science Institute, University of Manchester (United Kingdom)

    2014-06-23

    We report the uranium(VI) carbene imido oxo complex [U(BIPM{sup TMS})(NMes)(O)(DMAP){sub 2}] (5, BIPM{sup TMS}=C(PPh{sub 2}NSiMe{sub 3}){sub 2}; Mes=2,4,6-Me{sub 3}C{sub 6}H{sub 2}; DMAP=4-(dimethylamino)pyridine) which exhibits the unprecedented arrangement of three formal multiply bonded ligands to one metal center where the coordinated heteroatoms derive from different element groups. This complex was prepared by incorporation of carbene, imido, and then oxo groups at the uranium center by salt elimination, protonolysis, and two-electron oxidation, respectively. The oxo and imido groups adopt axial positions in a T-shaped motif with respect to the carbene, which is consistent with an inverse trans-influence. Complex 5 reacts with tert-butylisocyanate at the imido rather than carbene group to afford the uranyl(VI) carbene complex [U(BIPM{sup TMS})(O){sub 2}(DMAP){sub 2}] (6). (copyright 2014 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  19. Synthesis and structures of bimetallic titanium and chromium carbene complexes of the type Cp/sub 2/Ti(Cl)O(CH/sub 3/)CCr(CO)/sub 5/

    Energy Technology Data Exchange (ETDEWEB)

    Anslyn, E.V.; Santarsiero, B.D.; Grubbs, R.H.

    1988-10-01

    Insertion reactions are some of the most common and important reactions in organometallic chemistry. Aside from being mechanistically interesting, they have proven useful in organic synthesis and have been postulated in catalytic cycles. A subset of the broad group of insertion reactions is the insertion of carbon monoxides of group VIB metal carbonyl complexes into early-transition-metal alkyl, aryl and hydride bonds. Although the coupling of metal alkylidenes with metal carbonyl complexes is rare in monometallic systems, such coupling is frequently postulated in heterogeneous Fischer-Tropsch systems to yield surface-bound ketene fragments. The formation of bound ketene in bimetallic and cluster complexes has been documented. Herein the authors report the coupling of titanocene methylidene with Cr(CO)/sub 6/ to yield a titanocene ketene complex.

  20. From betaines to anionic N-heterocyclic carbenes. Borane, gold, rhodium, and nickel complexes starting from an imidazoliumphenolate and its carbene tautomer

    Directory of Open Access Journals (Sweden)

    Ming Liu

    2016-12-01

    Full Text Available The mesomeric betaine imidazolium-1-ylphenolate forms a borane adduct with tris(pentafluorophenylborane by coordination with the phenolate oxygen, whereas its NHC tautomer 1-(2-phenolimidazol-2-ylidene reacts with (triphenylphosphinegold(I chloride to give the cationic NHC complex [Au(NHC2][Cl] by coordination with the carbene carbon atom. The anionic N-heterocyclic carbene 1-(2-phenolateimidazol-2-ylidene gives the complexes [K][Au(NHC−2], [Rh(NHC−3] and [Ni(NHC−2], respectively. Results of four single crystal analyses are presented.

  1. Role of carbene complexes in initiation and chain propagation in double bond redistribution reactions

    International Nuclear Information System (INIS)

    Dolgoplosk, K.L.; Makovetskij, E.I.; Tinyakova, E.I.; Golenko, T.G.; Oreshkin, I.A.

    1976-01-01

    A study has been made of the role of carbene complexes of tungsten in initiation and propagation of the ring-opening polymerization of cycloolefins. Data are given on polymerization of cyclopentene and cycloocterdiene-1,5 in the presence of the system tungsten chloride-diazo-compound (DAC)

  2. Bis-ligated Ti and Zr complexes of chelating N-heterocyclic carbenes

    KAUST Repository

    El-Batta, Amer; Waltman, Andrew W.; Grubbs, Robert H.

    2011-01-01

    In this communication we report the synthesis of novel titanium and zirconium complexes ligated by bidentate "salicylaldimine-like" N-heterocyclic carbenes (NHC). Double addition of the NHC chelate to either TiCl4(thf)2 or ZrCl4 forms bis

  3. Synthesis in situ of gold nanoparticles by a dialkynyl Fischer carbene complex anchored to glass surfaces

    International Nuclear Information System (INIS)

    Bertolino, María Candelaria; Granados, Alejandro Manuel

    2016-01-01

    Highlights: • Fischer carbene 1-W reacts via cycloaddition without Cu(I) with azide terminal surface. • This reaction on the surface is regioselective to internal triple bond of 1-W. • 1-W bound to glass surface produce AuNps in situ fixed to the surface. • This ability is independent of how 1-W is bonded to the surface. • This hybrid surface can be valuable as SERS substrate or in heterogeneous catalysis. - Abstract: In this work we present a detailed study of classic reactions such as “click reaction” and nucleophilic substitution reaction but on glass solid surface (slides). We used different reactive center of a dialkynylalcoxy Fischer carbene complex of tungsten(0) to be anchored to modified glass surface with amine, to obtain aminocarbene, and azide terminal groups. These cycloaddition reaction showed regioselectivity to internal triple bond of dialkynyl Fischer carbene complex without Cu(I) as catalyst. Anyway the carbene anchored was able to act as a reducing agent to produce in situ very stable gold nanoparticles fixed on surface. We showed the characterization of modified glasses by contact angle measurements and XPS. Synthesized nanoparticles were characterized by SEM, XPS, EDS and UV–vis. The modified glasses showed an important enhancement Raman-SERS. This simple, fast and robust method to create a polifunctional and hybrid surfaces can be valuable in a wide range of applications such as Raman-SERS substrates and other optical fields.

  4. Abstraction of methyl from neutral Fischer-type carbene complexes: A new site for nucleophilic attack

    Energy Technology Data Exchange (ETDEWEB)

    Toomey, L.M.; Atwood, J.D. [State Univ. of New York, Buffalo, NY (United States)

    1997-02-04

    Reactions of Fischer-type carbene complexes, M(CO){sub 5}(C(OMe)pH) (M = Cr, W), with metal carbonyl anions (M`{sup -} = CpFe(CO){sub 2}{sup -@}, Re(CO){sub 5}{sup -}, Mn(CO){sub 4}PPh{sub 3}{sup -}, Co(CO){sub 3}PPh{sub 3}{sup -}, Cp{sup *}Cr(CO){sub 3}{sup -}, CpMo(CO){sub 3}{sup -}) result in demethylation of the carbene complexes. The products are M(CO){sub 5}C(O)Ph{sup -} and M`-Me, characterized by infrared and NMR spectroscopy. A slower rate for reaction with W(CO){sub 5}(C(OEt)Ph) in comparison to the methyl analogue is consistent with nucleophilic attack of the metal carbonyl anion on the methyl of the methoxy group of the carbene. This is a new type of nucleophilic attack of a Fischer-type carbene. 22 refs., 1 fig., 1 tab.

  5. Synthesis in situ of gold nanoparticles by a dialkynyl Fischer carbene complex anchored to glass surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Bertolino, María Candelaria, E-mail: cbertolino@fcq.unc.edu.ar; Granados, Alejandro Manuel, E-mail: ale@fcq.unc.edu.ar

    2016-10-15

    Highlights: • Fischer carbene 1-W reacts via cycloaddition without Cu(I) with azide terminal surface. • This reaction on the surface is regioselective to internal triple bond of 1-W. • 1-W bound to glass surface produce AuNps in situ fixed to the surface. • This ability is independent of how 1-W is bonded to the surface. • This hybrid surface can be valuable as SERS substrate or in heterogeneous catalysis. - Abstract: In this work we present a detailed study of classic reactions such as “click reaction” and nucleophilic substitution reaction but on glass solid surface (slides). We used different reactive center of a dialkynylalcoxy Fischer carbene complex of tungsten(0) to be anchored to modified glass surface with amine, to obtain aminocarbene, and azide terminal groups. These cycloaddition reaction showed regioselectivity to internal triple bond of dialkynyl Fischer carbene complex without Cu(I) as catalyst. Anyway the carbene anchored was able to act as a reducing agent to produce in situ very stable gold nanoparticles fixed on surface. We showed the characterization of modified glasses by contact angle measurements and XPS. Synthesized nanoparticles were characterized by SEM, XPS, EDS and UV–vis. The modified glasses showed an important enhancement Raman-SERS. This simple, fast and robust method to create a polifunctional and hybrid surfaces can be valuable in a wide range of applications such as Raman-SERS substrates and other optical fields.

  6. Theoretical NMR spectroscopy of N-heterocyclic carbenes and their metal complexes

    KAUST Repository

    Falivene, Laura

    2016-12-26

    Recent theoretical analysis of the NMR properties of free N-heterocyclic carbenes (NHC) and Metal-NHC complexes has complemented experiments, allowing the establishment of structure/property relationships and the rationalization of otherwise surprising experimental results. In this review, the main conclusions from recent literature are discussed, with the aim to offer a vision of the potential of theoretical analyses of NMR properties.

  7. Amide Synthesis from Alcohols and Amines Catalyzed by Ruthenium N-Heterocyclic Carbene Complexes

    DEFF Research Database (Denmark)

    Dam, Johan Hygum; Osztrovszky, Gyorgyi; Nordstrøm, Lars Ulrik Rubæk

    2010-01-01

    The direct synthesis of amides from alcohols and amines is described with the simultaneous liberation of dihydrogen. The reaction does not require any stoichiometric additives or hydrogen acceptors and is catalyzed by ruthenium N-heterocyclic carbene complexes. Three different catalyst systems...... are presented that all employ 1,3-diisopropylimidazol-2-ylidene (IiPr) as the carbene ligand. In addition, potassium tert-butoxide and a tricycloalkylphosphine are required for the amidation to proceed. In the first system, the active catalyst is generated in situ from [RuCl2(cod)] (cod = 1,5-cyclooctadiene), 1...... chloride and base. A range of different primary alcohols and amines have been coupled in the presence of the three catalyst systems to afford the corresponding amides in moderate to excellent yields. The best results are obtained with sterically unhindered alcohols and amines. The three catalyst systems do...

  8. Bis-ligated Ti and Zr complexes of chelating N-heterocyclic carbenes

    KAUST Repository

    El-Batta, Amer

    2011-07-01

    In this communication we report the synthesis of novel titanium and zirconium complexes ligated by bidentate "salicylaldimine-like" N-heterocyclic carbenes (NHC). Double addition of the NHC chelate to either TiCl4(thf)2 or ZrCl4 forms bis-ligated organometallic fragments with a distorted octahedral geometry. These complexes are rare examples of group IV transition-metal NHC adducts. Preliminary catalytic tests demonstrate that in the presence of methylaluminoxane (MAO) these complexes are useful initiators for the polymerization of ethylene and the copolymerization of ethylene with norbornene and 1-octene. © 2011 Elsevier B.V. All rights reserved.

  9. Synthesis and Antimicrobial Activity of Novel Ag-N-Hetero-cyclic Carbene Complexes

    Directory of Open Access Journals (Sweden)

    İlknur Özdemir

    2010-04-01

    Full Text Available A series of imidazolidinium ligand precursors are metallated with Ag2O to give silver(I N-heterocyclic carbene complexes. All compounds were fully characterized by elemental analyses, 1H-NMR, 13C-NMR and IR spectroscopy techniques. All compounds studied in this work were screened for their in vitro antimicrobial activities against the standard strains: Enterococcus faecalis (ATCC 29212, Staphylococcus aureus (ATCC 29213, Escherichia coli (ATCC 25922, Pseudomonas aeruginosa (ATCC 27853 and the fungi Candida albicans and Candida tropicalis. The new imidazolidin-2-ylidene silver complexes have been found to display effective antimicrobial activity against a series of bacteria and fungi.

  10. Simple building-block route to (Phosphanyl-carbene)palladium complexes via intermolecular addition of functionalised phosphanes to isocyanides

    NARCIS (Netherlands)

    Eberhard, M.R.; van Vliet, Bart; Durán Páchon, L.; Rothenberg, G.; Eastham, G.; Kooijman, H.; Spek, A.L.; Elsevier, C.J.

    2009-01-01

    We present a straightforward protocol for making (phosphanyl- carbene)PdII complexes. These complexes have bidentate ligands containing an acyclic diamino- or aminooxycarbene and a phosphane. The synthesis gives good yields (typically 70–90%) for a variety of complexes (22 compounds). Moreover, it

  11. Reactivity of N-heterocyclic carbene-pyridine palladacyclopentadiene complexes toward halogen addition. The unpredictable course of the reaction.

    Science.gov (United States)

    Visentin, Fabiano; Santo, Claudio; Scattolin, Thomas; Demitri, Nicola; Canovese, Luciano

    2017-08-08

    As an extension of a previously published work we have reacted some palladacyclopentadiene complexes stabilized by bidentate N-heterocyclic carbene-pyridine or monodentate N-heterocyclic carbene-pyridine and isocyanide ligands with the halogens I 2 and Br 2 . All the bidentate and monodentate complexes react with halogens to give at first the expected σ-coordinated butadienyl fragment. However, two of the less hindered NHC carbene-pyridine bidentate butadienyl iodo derivatives undergo a further rearrangement and novel Pd(ii) complexes characterized by a ten term coordinative ring were isolated and characterized. In the most favorable case we were able to carry out the kinetics of rearrangement and measure its reaction rate. Moreover, we have surmised a plausible mechanism on the basis of a dedicated computational approach and in one case the surprising structure characterized by the ten term coordinative ring was resolved by X-ray diffraction.

  12. Reversible alkyne insertion in the benzannulation reaction of Fischer carbene complexes with alkynes

    Energy Technology Data Exchange (ETDEWEB)

    Waters, M.L.; Bos, M.E.; Wulff, W.D. [Univ. of Chicago, IL (United States)

    1995-12-31

    The benzannulation reaction of Fischer carbene complexes with alkynes to give phenols is highly regioselective with terminal alkynes, and reasonably regioselective with internal alkynes. This has been attributed to steric factors in intermediates, where one form is favored due to close contact between the R substituent and a cis-CO ligand. Whether alkyne insertion is kinetically or thermodynamically controlled has not been determined. The authors now have evidence from regioselectivity studies that alkyne insertion into the metal-carbon bond is reversible. Implications of these results and further mechanistic considerations will be presented.

  13. Cationic bis-N-heterocyclic carbene (NHC) ruthenium complex: Structure and application as latent catalyst in olefin metathesis

    KAUST Repository

    Rouen, Mathieu

    2014-09-11

    An unexpected cationic bis-N-heterocyclic carbene (NHC) benzylidene ether based ruthenium complex (2 a) was prepared through the double incorporation of an unsymmetrical unsaturated N-heterocyclic carbene (U2-NHC) ligand that bore an N-substituted cyclododecyl side chain. The isolation and full characterization (including X-ray diffraction studies) of key synthetic intermediates along with theoretical calculations allowed us to understand the mechanism of the overall cationization process. Finally, the newly developed complex 2 a displayed interesting latent behavior during ring-closing metathesis, which could be "switched on" under acidic conditions.

  14. Synthesis, characterization, and reactivity of furan- and thiophene-functionalized bis(n-heterocyclic carbene) complexes of iron(II)

    KAUST Repository

    Rieb, Julia; Raba, Andreas; Haslinger, Stefan; Kaspar, Manuel; Pö thig, Alexander; Cokoja, Mirza; Basset, Jean-Marie; Kü hn, Fritz

    2014-01-01

    The synthesis of iron(II) complexes bearing new heteroatom-functionalized methylene-bridged bis(N-heterocyclic carbene) ligands is reported. All complexes are characterized by single-crystal X-ray diffraction (SC-XRD), nuclear magnetic resonance

  15. N-Heterocyclic Carbene Complexes in Dehalogenation Reactions

    Science.gov (United States)

    Mas-Marzá, Elena; Page, Michael J.; Whittlesey, Michael K.

    Catalytic dehalogenation represents an underdeveloped transformation in M-NHC chemistry with a small number of reports detailing the reactivity of Co, Ru, Ni and Pd catalysts. In situ generated nickel and palladium NHC complexes catalyse the hydrodechlorination of aryl chlorides. Lower coordinate Ni complexes are proposed to operate in the hydrodefluorination of mono- and poly-fluorinated substrates. The single example of Ru-NHC catalysed hydrodefluorination of fully and partially fluorinated aromatic substrates is characterised by an unusual regioselectivity. The highly regioselective dehydrohalogenation of relatively unreactive alkyl halide substrates is achieved with a cobalt NHC catalyst.

  16. Cyclopentadienyl molybdenum(II/VI) N-heterocyclic carbene complexes: Synthesis, structure, and reactivity under oxidative conditions

    KAUST Repository

    Li, Shenyu; Kee, Choonwee; Huang, Kuo-Wei; Hor, Andy Sum Andy; Zhao, Jin

    2010-01-01

    A series of N-heterocyclic carbene (NHC) complexes CpMo(CO) 2(NHC)X (NHC = IMe = 1,3-dimethylimidazol-2-ylidene, X = Br, 1; NHC = 1,3-dipropylimidazol-2-ylidene, X = Br, 2; NHC = IMes = 1,3-bis(2,4,6- trimethylphenyl)imidazol-2-ylidene, X = Br, 3

  17. Synthesis of naphthalenes through three-component coupling of alkynes, Fischer carbene complexes, and benzaldehyde hydrazones via isoindole intermediates.

    Science.gov (United States)

    Duan, Shaofeng; Sinha-Mahapatra, Dilip K; Herndon, James W

    2008-04-17

    The synthesis of naphthalene derivatives through three-component coupling of 2-alkynylbenzaldehyde hydrazones with carbene complexes and electron-deficient alkynes has been examined. The reaction involves formation of an isoindole derivative, followed by intramolecular Diels-Alder reaction, followed by nitrene extrusion. The reaction was highly regioselective using unsymmetrical alkynes.

  18. Synthesis of Naphthalenes through Three-Component Coupling of Alkynes, Fischer Carbene Complexes, and Benzaldehyde Hydrazones via Isoindole Intermediates

    Science.gov (United States)

    Duan, Shaofeng; Sinha-Mahapatra, Dilip K.; Herndon, James W.

    2008-01-01

    The synthesis of naphthalene derivatives through three-component coupling of 2-alkynylbenzaldehyde hydrazones with carbene complexes and electron-deficient alkynes has been examined. The reaction involves formation of an isoindole derivative, followed by intramolecular Diels–Alder reaction, followed by nitrene extrusion. The reaction was highly regioselective using unsymmetrical alkynes. PMID:18351767

  19. Synthesis of Naphthalenes through Three-Component Coupling of Alkynes, Fischer Carbene Complexes, and Benzaldehyde Hydrazones via Isoindole Intermediates

    OpenAIRE

    Duan, Shaofeng; Sinha-Mahapatra, Dilip K.; Herndon, James W.

    2008-01-01

    The synthesis of naphthalene derivatives through three-component coupling of 2-alkynylbenzaldehyde hydrazones with carbene complexes and electron-deficient alkynes has been examined. The reaction involves formation of an isoindole derivative, followed by intramolecular Diels–Alder reaction, followed by nitrene extrusion. The reaction was highly regioselective using unsymmetrical alkynes.

  20. Synthesis, characterization, and reactivity of furan- and thiophene-functionalized bis(n-heterocyclic carbene) complexes of iron(II)

    KAUST Repository

    Rieb, Julia

    2014-09-15

    The synthesis of iron(II) complexes bearing new heteroatom-functionalized methylene-bridged bis(N-heterocyclic carbene) ligands is reported. All complexes are characterized by single-crystal X-ray diffraction (SC-XRD), nuclear magnetic resonance (NMR) spectroscopy, and elemental analysis. Tetrakis(acetonitrile)-cis-[bis(o-imidazol-2-ylidenefuran)methane]iron(II) hexafluorophosphate (2a) and tetrakis(acetonitrile)-cis-[bis(o-imidazol-2-ylidenethiophene)methane]iron(II) hexafluorophosphate (2b) were obtained by aminolysis of [Fe{N(SiMe3)2}2(THF)] with furan- and thiophene-functionalized bis(imidazolium) salts 1a and 1b in acetonitrile. The SC-XRD structures of 2a and 2b show coordination of the bis(carbene) ligand in a bidentate fashion instead of a possible tetradentate coordination. The four other coordination sites of these distorted octahedral complexes are occupied by acetonitrile ligands. Crystallization of 2a in an acetone solution by the slow diffusion of Et2O led to the formation of cisdiacetonitriledi[ bis(o-imidazol-2-ylidenefuran)methane]iron(II) hexafluorophosphate (3a) with two bis(carbene) ligands coordinated in a bidentate manner and two cis-positioned acetonitrile molecules. Compounds 2a and 2b are the first reported iron(II) carbene complexes with four coordination sites occupied by solvent molecules, and it was demonstrated that those solvent ligands can undergo ligand-exchange reactions.

  1. N-heterocyclic carbene metal complexes as bio-organometallic antimicrobial and anticancer drugs.

    Science.gov (United States)

    Patil, Siddappa A; Patil, Shivaputra A; Patil, Renukadevi; Keri, Rangappa S; Budagumpi, Srinivasa; Balakrishna, Geetha R; Tacke, Matthias

    2015-01-01

    Late transition metal complexes that bear N-heterocyclic carbene (NHC) ligands have seen a speedy growth in their use as both, metal-based drug candidates and potentially active homogeneous catalysts in a plethora of C-C and C-N bond forming reactions. This review article focuses on the recent developments and advances in preparation and characterization of NHC-metal complexes (metal: silver, gold, copper, palladium, nickel and ruthenium) and their biomedical applications. Their design, syntheses and characterization have been reviewed and correlated to their antimicrobial and anticancer efficacies. All these initial discoveries help validate the great potential of NHC-metal derivatives as a class of effective antimicrobial and anticancer agents.

  2. Dimerisation, rhodium complex formation and rearrangements of N-heterocyclic carbenes of indazoles

    Directory of Open Access Journals (Sweden)

    Zong Guan

    2014-04-01

    Full Text Available Deprotonation of indazolium salts at low temperatures gives N-heterocyclic carbenes of indazoles (indazol-3-ylidenes which can be trapped as rhodium complexes (X-ray analysis. In the absence of Rh, the indazol-3-ylidenes spontaneously dimerize under ring cleavage of one of the N,N-bonds and ring closure to an indazole–indole spiro compound which possesses an exocyclic imine group. The E/Z isomers of the imines can be separated by column chromatography when methanol is used as eluent. We present results of a single crystal X-ray analysis of one of the E-isomers, which equilibrate in solution as well as in the solid state. Heating of the indazole–indole spiro compounds results in the formation of quinazolines by a ring-cleavage/ring-closure sequence (X-ray analysis. Results of DFT calculations are presented.

  3. Rare-earth- and uranium-mesoionic carbenes. A new class of f-block carbene complex derived from an N-heterocyclic olefin

    Energy Technology Data Exchange (ETDEWEB)

    Seed, John A.; Gregson, Matthew; Chilton, Nicholas F.; Wooles, Ashley J.; Liddle, Stephen T. [School of Chemistry, The University of Manchester (United Kingdom); Tuna, Floriana; McInnes, Eric J.L. [School of Chemistry and Photon Science Institute, The University of Manchester (United Kingdom)

    2017-09-11

    Neutral mesoionic carbenes (MICs) have emerged as an important class of carbene, however they are found in the free form or ligated to only a few d-block ions. Unprecedented f-block MIC complexes [M(N''){sub 3}{CN(Me)C(Me)N(Me)CH}] (M=U, Y, La, Nd; N''=N(SiMe{sub 3}){sub 2}) are reported. These complexes were prepared by a formal 1,4-proton migration reaction when the metal triamides [M(N''){sub 3}] were treated with the N-heterocyclic olefin H{sub 2}C=C(NMeCH){sub 2}, which constitutes a new, general way to prepare MIC complexes. Quantum chemical calculations on the 5f{sup 3} uranium(III) complex suggest the presence of a U=C donor-acceptor bond, composed of a MIC→U σ-component and a U(5f)→MIC(2p) π-back-bond, but for the d{sup 0}f{sup 0} Y and La and 4f{sup 3} Nd congeners only MIC→M σ-bonding is found. Considering the generally negligible π-acidity of MICs, this is surprising and highlights that greater consideration should possibly be given to recognizing MICs as potential π-acid ligands when coordinated to strongly reducing metals. (copyright 2017 The Authors. Published by Wiley-VCH Verlag GmbH and Co. KGaA.)

  4. Alkyne-Azide Cycloaddition Catalyzed by Silver Chloride and “Abnormal” Silver N-Heterocyclic Carbene Complex

    Directory of Open Access Journals (Sweden)

    Aldo I. Ortega-Arizmendi

    2013-01-01

    Full Text Available A library of 1,2,3-triazoles was synthesized from diverse alkynes and azides using catalytic amounts of silver chloride instead of copper compounds. In addition, a novel “abnormal” silver N-heterocyclic carbene complex was tested as catalyst in this process. The results suggest that the reaction requires only 0.5% of silver complex, affording 1,2,3-triazoles in good yields.

  5. Synthesis and crystal structure of the iridium(I) carbene complex with a pair of hydrogen wing tips

    Energy Technology Data Exchange (ETDEWEB)

    Huang, H.-Y.; Chen, Z.-M.; Wang, Y.; Wu, E.-M.; Wang, G. [Jiangsu Institute of Nuclear Medicine, Ministry of Health, Key Laboratory of Molecular Nuclear Medicine (China); Jiang, M.-J., E-mail: jmj16888@126.com [Nanjing Medical University, Affiliated Wuxi Peoples Hospital, Wuxi Institute of Translational Medicine, Department of Clinical Laboratory Science (China)

    2016-12-15

    The iridium(I) cyclooctadiene complex with two (3-tert-butylimidazol-2-ylidene) ligands [(H-Im{sup t}Bu){sub 2}Ir(COD)]{sup +}PF{sub 6}{sup −} (C{sub 22}H{sub 32}PF{sub 6}IrN{sub 4}) has been prepared, and its crystal structure is determined by X-ray diffraction. Complex exhibits slightly distorted square planar configurations around the metal atom, which is coordinated by two H-Im{sup t}Bu ligands and one cyclooctadiene group. The new iridium carbene complex has a pair of hydrogen wing tips. The Ir−C{sub carbene} bond lengths are 2.066(5) and 2.052(5) Å, and the bond angle C−Ir−C between these bonds is 95.54(19)°. The dihedral angle between two imidazol-2-ylidene rings is 86.42°.

  6. Anti-trypanosomal activity of cationic N-heterocyclic carbene gold(I) complexes.

    Science.gov (United States)

    Winter, Isabel; Lockhauserbäumer, Julia; Lallinger-Kube, Gertrud; Schobert, Rainer; Ersfeld, Klaus; Biersack, Bernhard

    2017-06-01

    Two gold(I) N-heterocyclic carbene complexes 1a and 1b were tested for their anti-trypanosomal activity against Trypanosoma brucei parasites. Both gold compounds exhibited excellent anti-trypanosomal activity (IC 50 =0.9-3.0nM). The effects of the gold complexes 1a and 1b on the T. b. brucei cytoskeleton were evaluated. Rapid detachment of the flagellum from the cell body occurred after treatment with the gold complexes. In addition, a quick and complete degeneration of the parasitic cytoskeleton was induced by the gold complexes, only the microtubules of the detached flagellum remained intact. Both gold compounds 1a and 1b feature selective anti-trypanosomal agents and were distinctly more active against T. b. brucei cells than against human HeLa cells. Thus, the gold complexes 1a and 1b feature promising drug candidates for the treatment of trypanosome infections such as sleeping sickness (human African Trypanosomiasis caused by Trypanosoma brucei parasites). Copyright © 2017 Elsevier B.V. All rights reserved.

  7. Cyclometalated N-heterocyclic carbene iridium(iii) complexes with naphthalimide chromophores: a novel class of phosphorescent heteroleptic compounds.

    Science.gov (United States)

    Lanoë, Pierre-Henri; Chan, Jonny; Groué, Antoine; Gontard, Geoffrey; Jutand, Anny; Rager, Marie-Noelle; Armaroli, Nicola; Monti, Filippo; Barbieri, Andrea; Amouri, Hani

    2018-03-06

    A series of cyclometalated N-heterocyclic carbene complexes of the general formula [Ir(C^N) 2 (C^C:)] has been prepared. Two sets of compounds were designed, those where (C^C:) represents a bidentate naphthalimide-substituted imidazolylidene ligand and (C^N) = ppy (3a), F2ppy (4a), bzq (5a) and those where (C^C:) represents a naphthalimide-substituted benzimidazolylidene ligand and (C^N) = ppy (3b), F2ppy (4b), bzq (5b). The naphthalimide-imidazole and naphthalimide-benzimidazole ligands 1a,b and the related imidazolium and benzimidazolium salts 2a,b were also prepared and fully characterized. The N-heterocyclic carbene Ir(iii) complexes have been characterized by NMR spectroscopy, cyclic voltammetry and elemental analysis. Moreover, the molecular structures of one imidazolium salt and four Ir(iii) complexes were determined by single-crystal X-ray diffraction. The structures provide us with valuable information, most notably the orientation of the naphthalimide chromophore with respect to the N-heterocyclic carbene moiety. All compounds are luminescent at room temperature and in a frozen solvent at 77 K, exhibiting a broad emission band that extends beyond 700 nm. The presence of the naphthalimide moiety changes the character of the lowest excited state from 3 MLCT to 3 LC, as corroborated by DFT and TD-DFT calculations. Remarkably, replacing imidazole with a benzimidazole unit improves the quantum yields of these compounds by decreasing the k nr values which is an important feature for optimized emission performance. These studies provide valuable insights about a novel class of N-heterocyclic carbene-based luminescent complexes containing organic chromophores and affording metal complexes emitting across the red-NIR range.

  8. One-pot three-component synthesis of quinoxaline and phenazine ring systems using Fischer carbene complexes

    Directory of Open Access Journals (Sweden)

    Priyabrata Roy

    2010-05-01

    Full Text Available One-pot three-component coupling of o-alkynylheteroaryl carbonyl derivatives with Fischer carbene complexes and dienophiles leading to the synthesis of quinoxaline and phenazine ring systems has been investigated. This involves the generation of furo[3,4-b]pyrazine and furo[3,4-b]quinoxaline as transient intermediates, which were trapped with Diels–Alder dienophiles. This is the first report on furo[3,4-b]pyrazine intermediates.

  9. The inverse-trans-influence in tetravalent lanthanide and actinide bis(carbene) complexes

    Science.gov (United States)

    Gregson, Matthew; Lu, Erli; Mills, David P.; Tuna, Floriana; McInnes, Eric J. L.; Hennig, Christoph; Scheinost, Andreas C.; McMaster, Jonathan; Lewis, William; Blake, Alexander J.; Kerridge, Andrew; Liddle, Stephen T.

    2017-02-01

    Across the periodic table the trans-influence operates, whereby tightly bonded ligands selectively lengthen mutually trans metal-ligand bonds. Conversely, in high oxidation state actinide complexes the inverse-trans-influence operates, where normally cis strongly donating ligands instead reside trans and actually reinforce each other. However, because the inverse-trans-influence is restricted to high-valent actinyls and a few uranium(V/VI) complexes, it has had limited scope in an area with few unifying rules. Here we report tetravalent cerium, uranium and thorium bis(carbene) complexes with trans C=M=C cores where experimental and theoretical data suggest the presence of an inverse-trans-influence. Studies of hypothetical praseodymium(IV) and terbium(IV) analogues suggest the inverse-trans-influence may extend to these ions but it also diminishes significantly as the 4f orbitals are populated. This work suggests that the inverse-trans-influence may occur beyond high oxidation state 5f metals and hence could encompass mid-range oxidation state actinides and lanthanides. Thus, the inverse-trans-influence might be a more general f-block principle.

  10. Biological Screening of Newly Synthesized BIAN N-Heterocyclic Gold Carbene Complexes in Zebrafish Embryos

    Science.gov (United States)

    Farooq, Muhammad; Abu Taha, Nael; Butorac, Rachel R.; Evans, Daniel Anthony; Elzatahry, Ahmed A.; Elsayed, Elsayed Ahmed; Wadaan, Mohammad A. M.; Al-Deyab, Salem S.; Cowley, Alan H.

    2015-01-01

    N-Heterocyclic carbene (NHC) metal complexes possess diverse biological activities but have yet to be extensively explored as potential chemotherapeutic agents. We have previously reported the synthesis of a new class of NHC metal complexes N-heterocyclic with acetate [IPr(BIAN)AuOAc] and chloride [IPr(BIAN)AuCl] ligands. In the experiments reported herein, the zebrafish embryos were exposed to serial dilutions of each of these complexes for 10–12 h. One hundred percent mortality was observed at concentrations ≥50 µM. At sub-lethal concentrations (10–30 µM), both compounds influenced zebrafish embryonic development. However, quite diverse categories of abnormalities were found in exposed embryos with each compound. Severe brain deformation and notochord degeneration were evident in the case of [IPr(BIAN)AuOAc]. The zebrafish embryos treated with [IPr(BIAN)AuCl] exhibited stunted growth and consequently had smaller body sizes. A depletion of 30%–40% glutathione was detected in the treated embryos, which could account for one of the possible mechanism of neurotoxicity. The fact that these compounds are capable of both affecting the growth and also compromising antioxidant systems by elevating intracellular ROS production implies that they could play an important role as a new breed of therapeutic molecules. PMID:26501273

  11. Room-temperature hydrohydrazination of terminal alkynes catalyzed by saturated abnormal N-heterocyclic carbene-gold(I) complexes.

    Science.gov (United States)

    Manzano, Rubén; Wurm, Thomas; Rominger, Frank; Hashmi, A Stephen K

    2014-06-02

    A number of saturated abnormal N-heterocyclic carbene (NHC) complexes of gold, in combination with KBAr(F) 4 as activator, were successfully applied in the chemoselective addition of hydrazine to alkynes. The reaction proceeds even at room temperature, which was not possible to date with gold catalysts. The reaction can be applied to a number of substituted arylalkynes. With alkylalkynes the yields are low. The saturated abnormal NHC ligands are resistant to isomerization to the saturated normal NHC coordination mode under basic reaction conditions. Under acidic conditions, a simple protonation at the nitrogen atom not neighboring the carbene center was observed and unambiguously characterized by an X-ray crystal-structure analysis. Computational studies confirm that such an isomerization would be highly exothermic, the observed kinetic stability probably results from the need to shift two protons in such a process. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. A Rare Terminal Dinitrogen Complex of Chromium

    Energy Technology Data Exchange (ETDEWEB)

    Mock, Michael T.; Chen, Shentan; Rousseau, Roger J.; O' Hagan, Molly J.; Dougherty, William G.; Kassel, W. S.; DuBois, Daniel L.; Bullock, R. Morris

    2011-10-12

    The reduction of dinitrogen to ammonia from N2 and H2 is currently carried out by the Haber-Bosch process, an energy intensive process that requires high pressures and high temperatures and accounts for the production of millions of tons of ammonia per year. The development of a catalytic, energy-efficient process for N2 reduction is of great interest and remains a formidable challenge. In this communication, we are reporting the preparation, characterization and computational electronic structure analysis of a rare 'Chatt-type' ((P-P)2M(N2)2, P-P = diphosphine ligand) complex of chromium, cis-[Cr(N2)2(PPh2NBn2)2] and its reactivity with CO. This complex is supported by the diphosphine ligand PPh2NBn2, containing non-coordinating pendant amine bases, to serve as proton relays. Future studies for this complex are aimed at answering fundamental questions regarding the role of proton relays in the second coordination sphere in their ability to facilitate proton movement from an external acid to metal-bound dinitrogen ligands in the challenging multi-proton/electron reduction of N2 to ammonia.

  13. On the mechanism of imine elimination from Fischer tungsten carbene complexes

    Directory of Open Access Journals (Sweden)

    Philipp Veit

    2016-06-01

    Full Text Available (Aminoferrocenyl(ferrocenylcarbene(pentacarbonyltungsten(0 (CO5W=C(NHFcFc (W(CO5(E-2 is synthesized by nucleophilic substitution of the ethoxy group of (CO5W=C(OEtFc (M(CO5(1Et by ferrocenyl amide Fc-NH– (Fc = ferrocenyl. W(CO5(E-2 thermally and photochemically eliminates bulky E-1,2-diferrocenylimine (E-3 via a formal 1,2-H shift from the N to the carbene C atom. Kinetic and mechanistic studies to the formation of imine E-3 are performed by NMR, IR and UV–vis spectroscopy and liquid injection field desorption ionization (LIFDI mass spectrometry as well as by trapping experiments for low-coordinate tungsten complexes with triphenylphosphane. W(CO5(E-2 decays thermally in a first-order rate-law with a Gibbs free energy of activation of ΔG‡298K = 112 kJ mol−1. Three proposed mechanistic pathways are taken into account and supported by detailed (time-dependent densitiy functional theory [(TD-DFT] calculations. The preferred pathway is initiated by an irreversible CO dissociation, followed by an oxidative addition/pseudorotation/reductive elimination pathway with short-lived, elusive seven-coordinate hydrido tungsten(II intermediates cis(N,H-W(CO4(H(Z-15 and cis(C,H-W(CO4(H(Z-15.

  14. Late metal carbene complexes generated by multiple C-H activations: examining the continuum of M=C bond reactivity.

    Science.gov (United States)

    Whited, Matthew T; Grubbs, Robert H

    2009-10-20

    Unactivated C(sp(3))-H bonds are ubiquitous in organic chemicals and hydrocarbon feedstocks. However, these resources remain largely untapped, and the development of efficient homogeneous methods for hydrocarbon functionalization by C-H activation is an attractive and unresolved challenge for synthetic chemists. Transition-metal catalysis offers an attractive possible means for achieving selective, catalytic C-H functionalization given the thermodynamically favorable nature of many desirable partial oxidation schemes and the propensity of transition-metal complexes to cleave C-H bonds. Selective C-H activation, typically by a single cleavage event to produce M-C(sp(3)) products, is possible through myriad reported transition-metal species. In contrast, several recent reports have shown that late transition metals may react with certain substrates to perform multiple C-H activations, generating M=C(sp(2)) complexes for further elaboration. In light of the rich reactivity of metal-bound carbenes, such a route could open a new manifold of reactivity for catalytic C-H functionalization, and we have targeted this strategy in our studies. In this Account, we highlight several early examples of late transition-metal complexes that have been shown to generate metal-bound carbenes by multiple C-H activations and briefly examine factors leading to the selective generation of metal carbenes through this route. Using these reports as a backdrop, we focus on the double C-H activation of ethers and amines at iridium complexes supported by Ozerov's amidophosphine PNP ligand (PNP = [N(2-P(i)Pr(2)-4-Me-C(6)H(3))(2)](-)), allowing isolation of unusual square-planar iridium(I) carbenes. These species exhibit reactivity that is distinct from the archetypal Fischer and Schrock designations. We present experimental and theoretical studies showing that, like the classical square-planar iridium(I) organometallics, these complexes are best described as nucleophilic at iridium. We discuss

  15. Synthesis and Characterization of Ag(I) and Pd(II) Complexes with a Pyridine Substituted N-Heterocyclic Carbene Ligand

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Ga Young; Jung, Hyun Jin; Lee, Dong Heon [Chonbuk National Univ., Jeonju (Korea, Republic of); Park, Gyung Se [Kunsan National Univ., Kunsan (Korea, Republic of)

    2010-06-15

    We have used our new tridentate pyridine substituted N-heterocyclic carbene to generate an interesting trinuclear [((MepyCH{sub 2}){sub 2}-Im){sub 3}Ag{sub 3}]{sup 3+} complex, displaying very short Ag-Ag separations. A Pd(II)-NHC complex was prepared from [((MepyCH{sub 2}){sub 2}-Im){sub 3}Ag{sub 3}]{sup 3+} via a facile transmetallation, leading to a dimeric [(MepyCH{sub 2}){sub 2}-ImPdCl]{sub 2}{sup 2+} complex. Future plans are underway for the survey of the potential applications of these new NHC complexes as luminesent materials or homogeneous catalysts. Since Arduengo's discovery of the first isolable free carbene in 1991, N-heterocyclic carbenes (NHC) have been extensively utilized as ligands for transition metals. NHC are generally more stable than two extreme types of carbenes, the Fischer and the Schrock carbenes. They are good σ donors like most tertiary phosphins, PR{sub 3}, but the π-bonding with the metal is rather weak. The thriving studies of NHC-coordinated metal complexes produced a wide range of applications from homogeneous catalysts to materials science.

  16. Bioavailability of a potato chromium complex to the laboratory rat

    International Nuclear Information System (INIS)

    Gilbert, H.K.

    1985-01-01

    Research objectives were to study the effect of food source, preparation method and chemical form on bioavailability of chromium. Chromium concentration in potatoes was determined and tubers labeled either intrinsically or extrinsically with radioactive chromate. A labeled chromium complexes was isolated from preparations of raw, baked or fried potatoes and chromatographed on gel permeation media. Availability of the potato chromium complex to the rat was examined in three feeding studies. Animals were dosed with radioactive extrinsically or intrinsically labeled potato extract or with chromate. A labeled chromium complex was isolated from gastrointestinal contents of rats and chromatographed. Potato pulp and peel contained 1.63 and 2.70 μg Cr/g tissue respectively. True and apparent absorption from extrinsically labeled feedings were 33.4 +/- 4.7 and 29.8 +/- 11.2% respectively, and no differences existed between absorption from raw and cooked potatoes. Absorption from the extrinsic labeled potatoes differed significantly from absorption of inorganic chromatium. Apparent absorption of raw (11.1 +/- 7.9%) and cooked (-0.7 +/- 2.8%) intrinsically labeled feedings differed significantly. Absorption of inorganic chromium was 17.8% (true) and 11.5% (apparent). Examination of the chromium complex isolated from gastrointestinal tract contents showed enlargement of the complex in the stomach after consumption

  17. Recovery of Proteins and Chromium Complexes from Chromium – Containing Leather Waste (CCLW

    Directory of Open Access Journals (Sweden)

    B. Gutti

    2010-08-01

    Full Text Available Chromium – Containing Leather Waste (CCLW constitutes an environmental pollution problem to leather industries disposing the waste by landfill. The waste mainly consists of collagen and chromium III complexes. This work is a design of reactors to recover gelatin, polypeptides and chromium from CCLW. The results of the experiment shows that 68% of protein, based on dry weight of leather scraps, could be recovered. Three reactors with a total volume of 18 m3 was designed to handle 10,431 kg of waste generated from the tanning industries.

  18. Synthesis and characterization of an iron complex bearing a cyclic tetra-N-heterocyclic carbene ligand: An artifical heme analogue?

    KAUST Repository

    Anneser, Markus R.

    2015-04-20

    An iron(II) complex with a cyclic tetradentate ligand containing four N-heterocyclic carbenes was synthesized and characterized by means of NMR and IR spectroscopies, as well as by single-crystal X-ray structure analysis. The iron center exhibits an octahedral coordination geometry with two acetonitrile ligands in axial positions, showing structural analogies with porphyrine-ligated iron complexes. The acetonitrile ligands can readily be substituted by other ligands, for instance, dimethyl sulfoxide, carbon monoxide, and nitric oxide. Cyclic voltammetry was used to examine the electronic properties of the synthesized compounds. © 2015 American Chemical Society.

  19. Redox noninnocence of carbene ligands: carbene radicals in (catalytic) C-C bond formation

    NARCIS (Netherlands)

    Dzik, W.I.; Zhang, X.P.; de Bruin, B.

    2011-01-01

    In this Forum contribution, we highlight the radical-type reactivities of one-electron-reduced Fischer-type carbenes. Carbene complexes of group 6 transition metals (Cr, Mo, and W) can be relatively easily reduced by an external reducing agent, leading to one-electron reduction of the carbene ligand

  20. Synthesis and spectral properties of Chromium(III) complex of ...

    African Journals Online (AJOL)

    ISSCH) with chromium(III) chloride. The complex was characterized by molar conductance, magnetic moment, infrared, far-infrared and electronic spectra and elemental analysis. The ligand exists in keto tantomeric form and it coordinates through ...

  1. Aerosolized antimicrobial agents based on degradable dextran nanoparticles loaded with silver carbene complexes

    KAUST Repository

    Ornelas-Megiatto, Cá tia; Shah, Parth N.; Wich, Peter R.; Cohen, Jessica L.; Tagaev, Jasur A.; Smolen, Justin A.; Wright, Brian D.; Panzner, Matthew J.; Youngs, Wiley J.; Frechet, Jean; Cannon, Carolyn L.

    2012-01-01

    Degradable acetalated dextran (Ac-DEX) nanoparticles were prepared and loaded with a hydrophobic silver carbene complex (SCC) by a single-emulsion process. The resulting particles were characterized for morphology and size distribution using scanning electron microscopy (SEM), transmission electron microscopy (TEM), and dynamic light scattering (DLS). The average particle size and particle size distribution were found to be a function of the ratio of the organic phase to the surfactant containing aqueous phase with a 1:5 volume ratio of Ac-DEX CH2Cl2 (organic):PBS (aqueous) being optimal for the formulation of nanoparticles with an average size of 100 ± 40 nm and a low polydispersity. The SCC loading was found to increase with an increase in the SCC quantity in the initial feed used during particle formulation up to 30% (w/w); however, the encapsulation efficiency was observed to be the best at a feed ratio of 20% (w/w). In vitro efficacy testing of the SCC loaded Ac-DEX nanoparticles demonstrated their activity against both Gram-negative and Gram-positive bacteria; the nanoparticles inhibited the growth of every bacterial species tested. As expected, a higher concentration of drug was required to inhibit bacterial growth when the drug was encapsulated within the nanoparticle formulations compared with the free drug illustrating the desired depot release. Compared with free drug, the Ac-DEX nanoparticles were much more readily suspended in an aqueous phase and subsequently aerosolized, thus providing an effective method of pulmonary drug delivery. © 2012 American Chemical Society.

  2. Aerosolized antimicrobial agents based on degradable dextran nanoparticles loaded with silver carbene complexes.

    Science.gov (United States)

    Ornelas-Megiatto, Cátia; Shah, Parth N; Wich, Peter R; Cohen, Jessica L; Tagaev, Jasur A; Smolen, Justin A; Wright, Brian D; Panzner, Matthew J; Youngs, Wiley J; Fréchet, Jean M J; Cannon, Carolyn L

    2012-11-05

    Degradable acetalated dextran (Ac-DEX) nanoparticles were prepared and loaded with a hydrophobic silver carbene complex (SCC) by a single-emulsion process. The resulting particles were characterized for morphology and size distribution using scanning electron microscopy (SEM), transmission electron microscopy (TEM), and dynamic light scattering (DLS). The average particle size and particle size distribution were found to be a function of the ratio of the organic phase to the surfactant containing aqueous phase with a 1:5 volume ratio of Ac-DEX CH(2)Cl(2) (organic):PBS (aqueous) being optimal for the formulation of nanoparticles with an average size of 100 ± 40 nm and a low polydispersity. The SCC loading was found to increase with an increase in the SCC quantity in the initial feed used during particle formulation up to 30% (w/w); however, the encapsulation efficiency was observed to be the best at a feed ratio of 20% (w/w). In vitro efficacy testing of the SCC loaded Ac-DEX nanoparticles demonstrated their activity against both Gram-negative and Gram-positive bacteria; the nanoparticles inhibited the growth of every bacterial species tested. As expected, a higher concentration of drug was required to inhibit bacterial growth when the drug was encapsulated within the nanoparticle formulations compared with the free drug illustrating the desired depot release. Compared with free drug, the Ac-DEX nanoparticles were much more readily suspended in an aqueous phase and subsequently aerosolized, thus providing an effective method of pulmonary drug delivery.

  3. Aerosolized antimicrobial agents based on degradable dextran nanoparticles loaded with silver carbene complexes

    KAUST Repository

    Ornelas-Megiatto, Cátia

    2012-11-05

    Degradable acetalated dextran (Ac-DEX) nanoparticles were prepared and loaded with a hydrophobic silver carbene complex (SCC) by a single-emulsion process. The resulting particles were characterized for morphology and size distribution using scanning electron microscopy (SEM), transmission electron microscopy (TEM), and dynamic light scattering (DLS). The average particle size and particle size distribution were found to be a function of the ratio of the organic phase to the surfactant containing aqueous phase with a 1:5 volume ratio of Ac-DEX CH2Cl2 (organic):PBS (aqueous) being optimal for the formulation of nanoparticles with an average size of 100 ± 40 nm and a low polydispersity. The SCC loading was found to increase with an increase in the SCC quantity in the initial feed used during particle formulation up to 30% (w/w); however, the encapsulation efficiency was observed to be the best at a feed ratio of 20% (w/w). In vitro efficacy testing of the SCC loaded Ac-DEX nanoparticles demonstrated their activity against both Gram-negative and Gram-positive bacteria; the nanoparticles inhibited the growth of every bacterial species tested. As expected, a higher concentration of drug was required to inhibit bacterial growth when the drug was encapsulated within the nanoparticle formulations compared with the free drug illustrating the desired depot release. Compared with free drug, the Ac-DEX nanoparticles were much more readily suspended in an aqueous phase and subsequently aerosolized, thus providing an effective method of pulmonary drug delivery. © 2012 American Chemical Society.

  4. Synthesis, characterization and antimicrobial activities of novel silver(I) complexes with coumarin substituted N-heterocyclic carbene ligands.

    Science.gov (United States)

    Karataş, Mert Olgun; Olgundeniz, Begüm; Günal, Selami; Özdemir, İlknur; Alıcı, Bülent; Çetinkaya, Engin

    2016-02-15

    Eight new coumarin substituted silver(I) N-heterocyclic carbene (NHC) complexes were synthesized by the interaction of the corresponding imidazolium or benzimidazolium chlorides and Ag2O in dichloromethane at room temperature. Structures of these complexes were established on the basis of elemental analysis, (1)H NMR, (13)C NMR, IR and mass spectroscopic techniques. The antimicrobial activities of carbene precursors and silver NHC complexes were tested against standard strains: Enterococcus faecalis, Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa and the fungi Candida albicans and Candida tropicalis. Results showed that all the compounds inhibited the growth of the all bacteria and fungi strains and some complexes performed good activities against different microorganisms. Among all the compounds, the most lipophilic complex bis[1-(4-methylene-6,8-dimethyl-2H-chromen-2-one)-3-(naphthalene-2-ylmethyl)benzimidazol-2-ylidene]silver(I) dichloro argentate (5e) was found out as the most active one. Copyright © 2015 Elsevier Ltd. All rights reserved.

  5. Cyclopentadienyl molybdenum(II/VI) N-heterocyclic carbene complexes: Synthesis, structure, and reactivity under oxidative conditions

    KAUST Repository

    Li, Shenyu

    2010-04-26

    A series of N-heterocyclic carbene (NHC) complexes CpMo(CO) 2(NHC)X (NHC = IMe = 1,3-dimethylimidazol-2-ylidene, X = Br, 1; NHC = 1,3-dipropylimidazol-2-ylidene, X = Br, 2; NHC = IMes = 1,3-bis(2,4,6- trimethylphenyl)imidazol-2-ylidene, X = Br, 3; NHC = IBz = 1,3-dibenzylimidazol- 2-ylidene, X = Br, 4a, and X = Cl, 4b; NHC = 1-methyl-3-propylimidazol-2- ylidene, X = Br, 5) and [CpMo(CO)2(IMes)(CH3CN)][BF 4] (6) have been synthesized and fully characterized. The stability of metal-NHC ligand bonds in these compounds under oxidative conditions has been investigated. The thermally stable Mo(VI) dioxo NHC complex [CpMoO 2(IMes)][BF4] (9) has been isolated by the oxidation of the ionic complex 6 by TBHP (tert-butyl hydrogen peroxide). Complex 6 can be applied as a very active (TOFs up to 3400 h-1) and selective olefin epoxidation catalyst. While under oxidative conditions (in the presence of TBHP), compounds 1-5 decompose into imidazolium bromide and imidazolium polyoxomolybdate. The formation of polyoxomolybdate as oxidation products had not been observed in a similar epoxidation catalyzed by Mo(II) and Mo(VI) complexes. DFT studies suggest that the presence of Br- destabilizes the CpMo(VI) oxo NHC carbene species, consistent with the experimental observations. © 2010 American Chemical Society.

  6. A facile route to ruthenium-carbene complexes and their application in furfural hydrogenation

    NARCIS (Netherlands)

    Strassberger, Z.; Mooijman, M.; Ruijter, E.; Alberts, A.H.; de Graaff, C.; Orru, R.V.A.; Rothenberg, G.

    2010-01-01

    A number of new N-heterocyclic carbene (NHC) ligands were synthesized via a multicomponent reaction, wherein an aldehyde or ketone, a primary amine and an α-acidic isocyanide were reacted, giving the corresponding 2H-2-imidazolines. These were easily alkylated with an alkyl halide at position N-3,

  7. Dehydrogenative Synthesis of Imines from Alcohols and Amines Catalyzed by a Ruthenium N-Heterocyclic Carbene Complex

    DEFF Research Database (Denmark)

    Maggi, Agnese; Madsen, Robert

    2012-01-01

    A new method for the direct synthesis of imines from alcohols and amines is described where hydrogen gas is liberated. The reaction is catalyzed by the ruthenium N-heterocyclic carbene complex [RuCl2(IiPr)(p-cymene)] in the presence of the ligand DABCO and molecular sieves. The imination can...... be applied to a variety of primary alcohols and amines and can be combined with a subsequent addition reaction. A deuterium labeling experiment indicates that the catalytically active species is a ruthenium dihydride. The reaction is believed to proceed by initial dehydrogenation of the alcohol...

  8. Carbene complexes of zirconium. Synthesis, structure, and reactivity with carbon monoxide to affort coordinated ketene

    International Nuclear Information System (INIS)

    Barger, P.T.; Santarsiero, B.D.; Armantrout, J.; Bercaw, J.E.

    1984-01-01

    Treatment of Cp 2 Zr(L)(CO) (Cp = C 5 H 5 ; L = PMe 3 , CO) with Cp* 2 ZrH 2 (Cp* = C 5 Me 5 ) affords zirconium oxycarbene complexes, Cp 2 (L)Zr double bond CHO single bond Zr(X)Cp* 2 (L = PMe 3 , X = H, I; L = CO, X = H), that represent some of the first examples of group 4 metal-to-carbon multiple bonding. The first X-ray diffraction structure determination of a zirconium carbene complex, that of Cp(PMe 3 )Zr double bond CHO single bond Zr(H)Cp* 2 .C 6 H 6 , is reported (C2/c, a = 27.318 (4) A, b = 19.895 (3) A, c = 19.932 (5) A β = 132.188 (10) 0 , Z = 8) and shows a very short Zr-C bond length of 2.117 (7) A. Treatment of Cp 2 (CO)Zr double bond CHO single bond Zr(H)Cp* 2 with CH 3 I or Cp 2 (PMe 3 )Zr double bond CHO single bond Zr(I)Cp* 2 with CO affords the zirconium substituted enediolate zirconacycle, Cp* 2 ZrOCH double bond C(Zr(I)Cp 2 )O, which has been characterized by an X-ray diffraction study (P2 1 /c, a = 15.866 (4) A, b = 10.673 (3) A, c = 20.561 (4) A, β = 105.5 (2) 0 , Z = 4). This complex most likely forms by coupling of the zirconoxycarbene and a carbonyl to give a metal-coordinated ketene intermediate that subsequently rearranges to the isolated product. An isotopic crossover experiment has demonstrated that the new carbon-carbon bond is formed in an intramolecular coupling step. The ketene intermediate can be trapped by dissolving Cp 2 (CO)Zr double bond CHO single bond Zr(H)Cp* 2 in pyridine, giving Cp 2 (py)Zr(O double bond C double bond CHOZr(I)Cp* 2 ). Treatment of the isolated ketene complex with CH 3 I in benzene gives the enediolate zirconocycle; in pyridine Cp 2 (py)Zr(O double bond C double bond CHOZr(I)Cp* 2 ) can be observed spectroscopically. 38 references, 4 figures, 5 tables

  9. Synthesis of Fischer carbene complexes of iridium by C-H bond activation of methyl and cyclic ethers: Evidence for reversible {alpha}-hydrogen migration

    Energy Technology Data Exchange (ETDEWEB)

    Luecke, H.F.; Arndtsen, B.A.; Burger, P.; Bergman, R.G. [Lawrence Berkeley Lab., CA (United States)]|[Univ. of California, Berkeley, CA (United States)

    1996-03-13

    We report here a mild and versatile route to Fischer carbene complexes of iridium via the activation of C-H bonds of methyl and cyclic ethers, along with our preliminary studies of this rare family of carbene complexes. Theoretical studies suggest that {alpha}-hydrogen migrations can be kinetically favorable if a coordinatively unsaturated species can be accessed. Thus, the lability of the triflate ligand presumably facilitates this process. Further evidence for the rapidity, as well as reversibility, of this rearrangement was obtained by NMR analysis. 20 refs.

  10. Anticancer Gold N-Heterocyclic Carbene Complexes: A Comparative in vitro and ex vivo Study.

    Science.gov (United States)

    Estrada-Ortiz, Natalia; Guarra, Federica; de Graaf, Inge A M; Marchetti, Lorella; de Jager, Marina H; Groothuis, Geny M M; Gabbiani, Chiara; Casini, Angela

    2017-09-07

    A series of organometallic Au I N-heterocyclic carbene (NHC) complexes was synthesized and characterized for anticancer activity in four human cancer cell lines. The compounds' toxicity in healthy tissue was determined using precision-cut kidney slices (PCKS) as a tool to determine the potential selectivity of the gold complexes ex vivo. All evaluated compounds presented cytotoxic activity toward the cancer cells in the nano- or low micromolar range. The mixed Au I NHC complex, (tert-butylethynyl)-1,3-bis-(2,6-diisopropylphenyl)imidazol-2-ylidene gold(I), bearing an alkynyl moiety as ancillary ligand, showed high cytotoxicity in cancer cells in vitro, while being barely toxic in healthy rat kidney tissues. The obtained results open new perspectives toward the design of mixed NHC-alkynyl gold complexes for cancer therapy. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Carbynes and carbenes in coordination chemistry: A new class of pentaammine and tetraammine complexes of osmium(II)

    Energy Technology Data Exchange (ETDEWEB)

    Hodges, L.M.; Sabat, M.; Harman, W.D. (Univ. of Virginia, Charlottesville (United States))

    1993-02-17

    Since their discovery by Fischer and co-workers in 1973, the study of transition-metal carbyne complexes and their role in alkyne metathesis has rapidly developed into a mature field. Although carbyne complexes are known for a diverse set of early- and mid-transition metals, the vast majority of these complexes contain carbon or phosphine [pi]-acids, or bulky alkoxide ligands, which limit the coordination number. We wish to report the first example of a carbyne species, as well as several heteroatom-carbene derivatives, in which the metal fragment, Os[sup II](NH[sub 3])[sub 5], provides a classical octahedral coordination environment. The carbyne [Os(NH[sub 3])[sub 5]([equivalent to]CPh)](OTf)[sub 3] (2) is synthesized in two steps from Os(NH[sub 3])[sub 5](OTf)[sub 3] and benzaledhyde dimethyl acetal.

  12. A multi-target caffeine derived rhodium(i) N-heterocyclic carbene complex: evaluation of the mechanism of action.

    Science.gov (United States)

    Zhang, Jing-Jing; Muenzner, Julienne K; Abu El Maaty, Mohamed A; Karge, Bianka; Schobert, Rainer; Wölfl, Stefan; Ott, Ingo

    2016-08-16

    A rhodium(i) and a ruthenium(ii) complex with a caffeine derived N-heterocyclic carbene (NHC) ligand were biologically investigated as organometallic conjugates consisting of a metal center and a naturally occurring moiety. While the ruthenium(ii) complex was largely inactive, the rhodium(i) NHC complex displayed selective cytotoxicity and significant anti-metastatic and in vivo anti-vascular activities and acted as both a mammalian and an E. coli thioredoxin reductase inhibitor. In HCT-116 cells it increased the reactive oxygen species level, leading to DNA damage, and it induced cell cycle arrest, decreased the mitochondrial membrane potential, and triggered apoptosis. This rhodium(i) NHC derivative thus represents a multi-target compound with promising anti-cancer potential.

  13. Titanocene–Gold Complexes Containing N-Heterocyclic Carbene Ligands Inhibit Growth of Prostate, Renal, and Colon Cancers in Vitro

    Science.gov (United States)

    2016-01-01

    We report on the synthesis, characterization, and stability studies of new titanocene complexes containing a methyl group and a carboxylate ligand (mba = −OC(O)-p-C6H4-S−) bound to gold(I)–N-heterocyclic carbene fragments through the thiolate group: [(η5-C5H5)2TiMe(μ-mba)Au(NHC)]. The cytotoxicities of the heterometallic compounds along with those of novel monometallic gold–N-heterocyclic carbene precursors [(NHC)Au(mbaH)] have been evaluated against renal, prostate, colon, and breast cancer cell lines. The highest activity and selectivity and a synergistic effect of the resulting heterometallic species was found for the prostate and colon cancer cell lines. The colocalization of both titanium and gold metals (1:1 ratio) in PC3 prostate cancer cells was demonstrated for the selected compound 5a, indicating the robustness of the heterometallic compound in vitro. We describe here preliminary mechanistic data involving studies on the interaction of selected mono- and bimetallic compounds with plasmid (pBR322) used as a model nucleic acid and the inhibition of thioredoxin reductase in PC3 prostate cancer cells. The heterometallic compounds, which are highly apoptotic, exhibit strong antimigratory effects on the prostate cancer cell line PC3. PMID:27182101

  14. 1,2,4-Triazole-based N-heterocyclic carbene complexes of gold(I): synthesis, characterization and biological activity

    Czech Academy of Sciences Publication Activity Database

    Turek, J.; Růžičková, Z.; Tloušťová, Eva; Mertlíková-Kaiserová, Helena; Günterová, Jana; Rulíšek, Lubomír; Růžička, A.

    2016-01-01

    Roč. 30, č. 5 (2016), s. 318-322 ISSN 0268-2605 R&D Projects: GA ČR(CZ) GA14-31419S; GA MŠk LO1302 Institutional support: RVO:61388963 Keywords : gold(I) complexes * N-heterocyclic carbenes * cytotoxicity * apoptosis Subject RIV: CC - Organic Chemistry Impact factor: 2.319, year: 2016

  15. Effect of tert-Butyl Functionalization on the Photoexcited Decay of a Fe(II)-N-Heterocyclic Carbene Complex

    DEFF Research Database (Denmark)

    Pápai, Mátyás Imre; Penfold, Thomas J.; Møller, Klaus Braagaard

    2016-01-01

    -vibronic quantum dynamics simulations on the Fe-N-heterocyclic carbene complex, [Fe(btbip)2]2+ (btbip = 2,6-bis(3-tert-butyl-imidazole-1-ylidene)pyridine). The results demonstrate that a relatively minor structural change compared to its parent complex, [Fe(bmip)2]2+ (bmip = 2,6-bis(3-methyl-imidazole-1-ylidene....... This occurs because the tert-butyl functionalization stabilizes the 1MC states, enabling the 1,3MLCT → 1MC population transfer to occur close to the Franck-Condon geometry, making the conversion very efficient. Subsequently, a spin cascade occurs within the MC manifold, leading to the population of triplet...

  16. Sequential Functionalization of Alkynes and Alkenes Catalyzed by Gold(I) and Palladium(II) N-Heterocyclic Carbene Complexes

    KAUST Repository

    Gó mez-Herrera, Alberto; Nahra, Fady; Brill, Marcel; Nolan, Steven P.; Cazin, Catherine S. J.

    2016-01-01

    The iodination of terminal alkynes for the synthesis of 1-iodoalkynes using N-iodosuccinimide in the presence of a AuI-NHC (NHC=N-heterocyclic carbene) catalyst is reported. A series of aromatic alkynes was transformed successfully into the corresponding 1-iodoalkynes in good to excellent yields under mild reaction conditions. The further use of these compounds as organic building blocks and the advantageous choice of metal-NHC complexes as catalysts for alkyne functionalization were further demonstrated by performing selective AuI-catalyzed hydrofluorination to yield (Z)-2-fluoro-1-iodoalkenes, followed by a Suzuki–Miyaura cross-coupling with aryl boronic acids catalyzed by a PdII-NHC complex to access trisubstituted (Z)-fluoroalkenes. All methodologies can be performed sequentially with only minor variations in the optimized individual reaction conditions, maintaining high efficiency and selectivity in all cases, which therefore, provides straightforward access to valuable fluorinated alkenes from commercially available terminal alkynes.

  17. Sequential Functionalization of Alkynes and Alkenes Catalyzed by Gold(I) and Palladium(II) N-Heterocyclic Carbene Complexes

    KAUST Repository

    Gómez-Herrera, Alberto

    2016-08-22

    The iodination of terminal alkynes for the synthesis of 1-iodoalkynes using N-iodosuccinimide in the presence of a AuI-NHC (NHC=N-heterocyclic carbene) catalyst is reported. A series of aromatic alkynes was transformed successfully into the corresponding 1-iodoalkynes in good to excellent yields under mild reaction conditions. The further use of these compounds as organic building blocks and the advantageous choice of metal-NHC complexes as catalysts for alkyne functionalization were further demonstrated by performing selective AuI-catalyzed hydrofluorination to yield (Z)-2-fluoro-1-iodoalkenes, followed by a Suzuki–Miyaura cross-coupling with aryl boronic acids catalyzed by a PdII-NHC complex to access trisubstituted (Z)-fluoroalkenes. All methodologies can be performed sequentially with only minor variations in the optimized individual reaction conditions, maintaining high efficiency and selectivity in all cases, which therefore, provides straightforward access to valuable fluorinated alkenes from commercially available terminal alkynes.

  18. Chromium

    Science.gov (United States)

    ... 2 Whole wheat bread, 2 slices 2 Red wine, 5 ounces 1–13 Apple, unpeeled, 1 medium ... chromium or a placebo) might simply show the benefits of supplementation in a chromium-deficient population. Overall, ...

  19. Synthesis and anticancer activity of silver(I)-N-heterocyclic carbene complexes derived from the natural xanthine products caffeine, theophylline and theobromine.

    Science.gov (United States)

    Mohamed, Heba A; Lake, Benjamin R M; Laing, Thomas; Phillips, Roger M; Willans, Charlotte E

    2015-04-28

    A new library of silver(I)-N-heterocyclic carbene complexes prepared from the natural products caffeine, theophylline and theobromine is reported. The complexes have been fully characterised using a combination of NMR spectroscopy, mass spectrometry, elemental analysis and X-ray diffraction analysis. Furthermore, the hydrophobicity of the complexes has been measured. The silver(I)-N-heterocyclic carbenes have been evaluated for their antiproliferative properties against a range of cancer cell lines of different histological types, and compared to cisplatin. The data shows different profiles of response when compared to cisplatin in the same panel of cells, indicating a different mechanism of action. Furthermore, it appears that the steric effect of the ligand and the hydrophobicity of the complex both play a role in the chemosensitivity of these compounds, with greater steric bulk and greater hydrophilicity delivering higher cytotoxicity.

  20. 40 CFR 721.2097 - Azo chromium complex dyestuff preparation (generic name).

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Azo chromium complex dyestuff... New Uses for Specific Chemical Substances § 721.2097 Azo chromium complex dyestuff preparation... substance identified generically as an azo chromium complex dyestuff preparation (PMN P-95-240) is subject...

  1. 40 CFR 721.981 - Substituted naphtholoazo-substituted naphthalenyl-substituted azonaphthol chromium complex.

    Science.gov (United States)

    2010-07-01

    ... naphthalenyl-substituted azonaphthol chromium complex. 721.981 Section 721.981 Protection of Environment...-substituted naphthalenyl-substituted azonaphthol chromium complex. (a) Chemical substance and significant new... naphtholoazo-substituted naphthalenyl-substituted azonaphthol chromium complex (PMN P-93-1631) is subject to...

  2. Theoretical Predictions of Redox Potentials of Fischer-Type Chromium Anninocarbene Complexes

    Czech Academy of Sciences Publication Activity Database

    Kvapilová, Hana; Hoskovcová, Irena; Ludvík, Jiří; Záliš, Stanislav

    2014-01-01

    Roč. 33, č. 18 (2014), s. 4964-4972 ISSN 0276-7333 R&D Projects: GA MŠk LD14129; GA ČR GA13-04630S Institutional support: RVO:61388955 Keywords : standard hydrogen electrode * density functional theory * metal carbene complexes Subject RIV: CG - Electrochemistry Impact factor: 4.126, year: 2014

  3. Insights Into the Carbene-Initiated Aggregation of [Fe(cot)2

    KAUST Repository

    Lavallo, Vincent; El-Batta, Amer; Bertrand, Guy; Grubbs, Robert H.

    2010-01-01

    Carbenes attack! Stable carbenes react with [Fe(cot)2] in very different ways. Whereas the classical N-heterocyclic carbenes induce the formation of tetra- and trimetallic iron clusters, abnormal NHCs and carbocyclic carbenes (BACs) form mono- and bimetallic iron complexes. Cyclic (alkyl)(amino)carbenes (CAACs) react with [Fe(cot)2] in a completely different manner, namely through outersphere [4+1] cycloaddition.

  4. Insights Into the Carbene-Initiated Aggregation of [Fe(cot)2

    KAUST Repository

    Lavallo, Vincent

    2010-11-25

    Carbenes attack! Stable carbenes react with [Fe(cot)2] in very different ways. Whereas the classical N-heterocyclic carbenes induce the formation of tetra- and trimetallic iron clusters, abnormal NHCs and carbocyclic carbenes (BACs) form mono- and bimetallic iron complexes. Cyclic (alkyl)(amino)carbenes (CAACs) react with [Fe(cot)2] in a completely different manner, namely through outersphere [4+1] cycloaddition.

  5. Synthesis, photo-, and electrochemistry of ruthenium bis(bipyridine) complexes comprising a N-heterocyclic carbene ligand.

    Science.gov (United States)

    Leigh, Vivienne; Ghattas, Wadih; Lalrempuia, Ralte; Müller-Bunz, Helge; Pryce, Mary T; Albrecht, Martin

    2013-05-06

    Analogues of [Ru(bpy)3](2+) were prepared in which one pyridine ligand site is substituted by a N-heterocyclic carbene (NHC) ligand, that is, either by an imidazolylidene with a variable wingtip group R (R = Me, 3a; R = Et, 3b; R = iPr, 3c), or by a benzimidazolylidene (Me wingtip group, 3d), or by a 1,2,3-triazolylidene (Me wingtip group, 3e). All complexes were characterized spectroscopically, photophysically, and electrochemically. An increase of the size of the wingtip groups from Me to Et or iPr groups distorts the octahedral geometry (NMR spectroscopy) and curtails the reversibility of the ruthenium oxidation. NHC ligands with methyl wingtip groups display reversible ruthenium oxidation at a potential that reflects the donor properties of the NHC ligand (triazolylidene > imidazolylidene > benzimidazolylidene). The most attractive properties were measured for the triazolylidene ruthenium complex 3e, featuring the smallest gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) in the series (2.41 eV), a slightly red-shifted absorption profile, and reasonable excited-state lifetime (188 ns) when compared to [Ru(bpy)3](2+). These features demonstrate the potential utility of triazolylidene ruthenium complexes as photosensitizers for solar energy conversion.

  6. A chemical-biological evaluation of rhodium(I) N-heterocyclic carbene complexes as prospective anticancer drugs.

    Science.gov (United States)

    Oehninger, Luciano; Küster, Laura Nadine; Schmidt, Claudia; Muñoz-Castro, Alvaro; Prokop, Aram; Ott, Ingo

    2013-12-23

    Rhodium(I) complexes bearing N-heterocyclic carbene (NHC) ligands have been widely used in catalytic chemistry, but there are very few reports of biological properties of these organometallics. A series of Rh(I)-NHC derivatives with 1,5-cyclooctadiene and CO as secondary ligands were synthesized, characterized, and biologically investigated as prospective antitumor drug candidates. Pronounced antiproliferative effects were noted for all complexes, along with moderate inhibitory activity of thioredoxin reductase (TrxR) and efficient binding to biomolecules (DNA, albumin). Biodistribution studies showed that the presence of albumin lowered the cellular uptake and confirmed the transport of rhodium into the nuclei. Changes in the mitochondrial membrane potential (MMP) were observed as well as DNA fragmentation in wild-type and daunorubicin- or vincristine-resistant Nalm-6 leukemia cells. Overall, these studies indicated that Rh(I)-NHC fragments could be used as partial structures of new antitumor agents, in particular in those drugs designed to address resistant malignant tissues. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. N-BUTYL SUBSTITUTED N-HETEROCYCLIC CARBENE-PD(II-PYRIDINE (PEPPSI COMPLEXES: SYNTHESIS, CHARACTERIZATION AND CATALYTIC ACTIVITY IN THE SUZUKI-MIYAURA REACTION

    Directory of Open Access Journals (Sweden)

    Rukiye Fırıncı

    2016-08-01

    Full Text Available A series of N-butyl substituted imidazolium salts, (1a-c and their pyridine enhanced precatalyst preparation stabilization and initiation (PEPPSI themed palladium N-heterocyclic carbene complexes (2a-c were synthesized and characterized. Pd-NHC complexes were fully determined by elemental analysis and spectroscopic. The synthesized complexes were tested in Suzuki-Miyaura cross-coupling reaction. These complexes were found to be efficient catalysts for the Suzuki-Miyaura reaction of phenylboronic acid with aryl bromides.

  8. 21 CFR 176.160 - Chromium (Cr III) complex of N-ethyl-N-heptadecylfluoro-octane sulfonyl glycine.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Chromium (Cr III) complex of N-ethyl-N... § 176.160 Chromium (Cr III) complex of N-ethyl-N-heptadecylfluoro-octane sulfonyl glycine. The chromium... by weight of the chromium (Cr III) complex of heptadecylfluoro-octane sulfonic acid may be safely...

  9. Synthesis and characterization of a cationic phthalimido-functionalized N-heterocyclic carbene complex of palladium(II) and its catalytic activity

    KAUST Repository

    Goh, Li Min Serena

    2014-01-29

    A cationic phthalimido-functionalized N-heterocyclic carbene (NHC) palladium(II) complex has been synthesized from [3-methyl-1-(2′- phthalimidoethyl)imidazolium] hexafluorophosphate ([NHCMe,PhtH] PF6) by transmetalation and isolated in 67 % yield. The title complex has been applied as catalyst in the Suzuki-Miyaura cross-coupling reaction under benign aqueous conditions. The catalyst is active without any observable initiation period. High average turnover frequencies (TOFs) of up to 55000 h-1 have been reached with catalyst concentrations as low as 0.01 mol-%. A cationic phthalimido-functionalized N-heterocyclic carbene (NHC) palladium(II) complex has been prepared in high yield. The complex was activated instantly, without an initiation period, in the Suzuki-Miyaura cross-coupling reaction under benign aqueous aerobic conditions. Turnover frequencies (TOFs) up to 55000 h-1, were achieved with 0.01 mol-% of the complex. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Synthesis and characterization of a cationic phthalimido-functionalized N-heterocyclic carbene complex of palladium(II) and its catalytic activity

    KAUST Repository

    Goh, Li Min Serena; Hogerl, Manuel Peter; Jokic̈, Nadežda B.; Tanase, Alexandrina D.; Bechlars, Bettina; Baratta, Walter; Mí nk, Já nos; Kü hn, Fritz

    2014-01-01

    A cationic phthalimido-functionalized N-heterocyclic carbene (NHC) palladium(II) complex has been synthesized from [3-methyl-1-(2′- phthalimidoethyl)imidazolium] hexafluorophosphate ([NHCMe,PhtH] PF6) by transmetalation and isolated in 67 % yield. The title complex has been applied as catalyst in the Suzuki-Miyaura cross-coupling reaction under benign aqueous conditions. The catalyst is active without any observable initiation period. High average turnover frequencies (TOFs) of up to 55000 h-1 have been reached with catalyst concentrations as low as 0.01 mol-%. A cationic phthalimido-functionalized N-heterocyclic carbene (NHC) palladium(II) complex has been prepared in high yield. The complex was activated instantly, without an initiation period, in the Suzuki-Miyaura cross-coupling reaction under benign aqueous aerobic conditions. Turnover frequencies (TOFs) up to 55000 h-1, were achieved with 0.01 mol-% of the complex. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Structure and spectroscopic properties of the dimeric copper(I) N-heterocyclic carbene complex [Cu₂(CNC(t-Bu))₂](PF₆)₂.

    Science.gov (United States)

    Riener, Korbinian; Pöthig, Alexander; Cokoja, Mirza; Herrmann, Wolfgang A; Kühn, Fritz E

    2015-08-01

    In recent years, the use of copper N-heterocyclic carbene (NHC) complexes has expanded to fields besides catalysis, namely medicinal chemistry and luminescence applications. In the latter case, multinuclear copper NHC compounds have attracted interest, however, the number of these complexes in the literature is still quite limited. Bis[μ-1,3-bis(3-tert-butylimidazolin-2-yliden-1-yl)pyridine]-1κ(4)C(2),N:N,C(2');2κ(4)C(2),N:N,C(2')-dicopper(I) bis(hexafluoridophosphate), [Cu2(C19H25N5)2](PF6)2, is a dimeric copper(I) complex bridged by two CNC, i.e. bis(N-heterocyclic carbene)pyridine, ligands. Each Cu(I) atom is almost linearly coordinated by two NHC ligands and interactions are observed between the pyridine N atoms and the metal centres, while no cuprophilic interactions were observed. Very strong absorption bands are evident in the UV-Vis spectrum at 236 and 274 nm, and an emission band is observed at 450 nm. The reported complex is a new example of a multinuclear copper NHC complex and a member of a compound class which has only rarely been reported.

  12. Synthesis of Well-Defined Copper "N"-Heterocyclic Carbene Complexes and Their Use as Catalysts for a "Click Reaction": A Multistep Experiment that Emphasizes the Role of Catalysis in Green Chemistry

    Science.gov (United States)

    Ison, Elon A.; Ison, Ana

    2012-01-01

    A multistep experiment for an advanced synthesis lab course that incorporates topics in organic-inorganic synthesis and catalysis and highlights green chemistry principles was developed. Students synthesized two "N"-heterocyclic carbene ligands, used them to prepare two well-defined copper(I) complexes and subsequently utilized the complexes as…

  13. Electronic bond tuning with heterocyclic carbenes

    KAUST Repository

    Falivene, Laura

    2013-01-01

    We discuss the impact of the nature of the heterocyclic carbene ring, when used as a complex forming ligand, on the relative stability of key intermediates in three typical Ru, Pd and Au promoted reactions. Results show that P-heterocyclic carbenes have a propensity to increase the bonding of the labile ligand and of the substrate in Ru-promoted olefin metathesis, whereas negligible impact is expected on the stability of the ruthenacycle intermediate. In the case of Pd cross-coupling reactions, dissociation of a P-heterocyclic carbene is easier than dissociation of the N-heterocyclic analogue. In the case of the Au-OH synthon, the Au-OH bond is weakened with the P-heterocyclic carbene ligands. A detailed energy decomposition analysis is performed to rationalize these results. © 2013 The Royal Society of Chemistry.

  14. Chemistry of Iron N -heterocyclic carbene complexes: Syntheses, structures, reactivities, and catalytic applications

    KAUST Repository

    Riener, Korbinian

    2014-05-28

    Iron is the most abundant transition metal in Earth\\'s crust. It is relatively inexpensive, not very toxic, and environmentally benign. Undoubtedly, due to the involvement in a multitude of biological processes, which heavily rely on the rich functionalities of iron-containing enzymes, iron is one of the most important elements in nature. Additionally, three-coordinate iron complexes have been reported during the past several years. In this review, the mentioned iron NHC complexes are categorized by their main structure and reactivity attributes. Thus, monocarbene and bis-monocarbene complexes are presented first. This class is subdivided into carbonyl, nitrosyl, and halide compounds followed by a brief section on other, more unconventional iron NHC motifs. Subsequently, donor-substituted complexes bearing bi-, tri-, tetra-, or even pentadentate ligands and further pincer as well as scorpionato motifs are described.

  15. Multicomponent synthesis of unsymmetrical unsaturated N-heterocyclic carbene precursors and their related transition-metal complexes

    KAUST Repository

    Queval, Pierre

    2013-12-04

    A low-cost, modular, and easily scalable multicomponent procedure affording access in good yields and excellent selectivity (up to 93 %) to a wide range of (a)chiral unsymmetrical 1-aryl-3-cycloalkyl-imidazolium salts is disclosed. Electronic and steric properties of the corresponding unsymmetrical unsaturated N-heterocyclic carbene (U2-NHC) ligands were evaluated and evidenced strong electron donor ability, high steric discrimination, and modular steric demand. A low-cost, modular, and easily scalable multicomponent procedure, affording access to a wide range of (a)chiral unsymmetrical 1-aryl-3-cycloalkyl- imidazolium salts in good yields and excellent selectivities, is disclosed. Electronic and steric properties of the corresponding unsymmetrical unsaturated N-heterocyclic carbene (U2-NHC) ligands were evaluated and evidenced strong electron-donor ability, high steric discrimination, and modular steric demand. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Deconstructing selectivity in the gold-promoted cyclization of alkynyl benzothioamides to six-membered mesoionic carbene or acyclic carbene complexes

    KAUST Repository

    Vummaleti, Sai V. C.; Falivene, Laura; Poater, Albert; Cavallo, Luigi

    2014-01-01

    We demonstrate that the experimentally observed switch in selectivity from 5-exo-dig to 6-endo-dig cyclization of an alkynyl substrate, promoted by Au I and AuIII complexes, is connected to a switch from thermodynamic to kinetic reaction control. The AuIII center pushes alkyne coordination toward a single Au-C(alkyne) σ-bond, conferring carbocationic character (and reactivity) to the distal alkyne C atom. © 2014 American Chemical Society.

  17. Deconstructing selectivity in the gold-promoted cyclization of alkynyl benzothioamides to six-membered mesoionic carbene or acyclic carbene complexes

    KAUST Repository

    Vummaleti, Sai V. C.

    2014-05-02

    We demonstrate that the experimentally observed switch in selectivity from 5-exo-dig to 6-endo-dig cyclization of an alkynyl substrate, promoted by Au I and AuIII complexes, is connected to a switch from thermodynamic to kinetic reaction control. The AuIII center pushes alkyne coordination toward a single Au-C(alkyne) σ-bond, conferring carbocationic character (and reactivity) to the distal alkyne C atom. © 2014 American Chemical Society.

  18. Mixed N-Heterocyclic Carbene-Bis(oxazolinyl)borato Rhodium and Iridium Complexes in Photochemical and Thermal Oxidative Addition Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Songchen [Ames Laboratory; Manna, Kuntal [Ames Laboratory; Ellern, Arkady [Ames Laboratory; Sadow, Aaron D [Ames Laboratory

    2014-12-08

    In order to facilitate oxidative addition chemistry of fac-coordinated rhodium(I) and iridium(I) compounds, carbene–bis(oxazolinyl)phenylborate proligands have been synthesized and reacted with organometallic precursors. Two proligands, PhB(OxMe2)2(ImtBuH) (H[1]; OxMe2 = 4,4-dimethyl-2-oxazoline; ImtBuH = 1-tert-butylimidazole) and PhB(OxMe2)2(ImMesH) (H[2]; ImMesH = 1-mesitylimidazole), are deprotonated with potassium benzyl to generate K[1] and K[2], and these potassium compounds serve as reagents for the synthesis of a series of rhodium and iridium complexes. Cyclooctadiene and dicarbonyl compounds {PhB(OxMe2)2ImtBu}Rh(η4-C8H12) (3), {PhB(OxMe2)2ImMes}Rh(η4-C8H12) (4), {PhB(OxMe2)2ImMes}Rh(CO)2 (5), {PhB(OxMe2)2ImMes}Ir(η4-C8H12) (6), and {PhB(OxMe2)2ImMes}Ir(CO)2 (7) are synthesized along with ToMM(η4-C8H12) (M = Rh (8); M = Ir (9); ToM = tris(4,4-dimethyl-2-oxazolinyl)phenylborate). The spectroscopic and structural properties and reactivity of this series of compounds show electronic and steric effects of substituents on the imidazole (tert-butyl vs mesityl), effects of replacing an oxazoline in ToM with a carbene donor, and the influence of the donor ligand (CO vs C8H12). The reactions of K[2] and [M(μ-Cl)(η2-C8H14)2]2 (M = Rh, Ir) provide {κ4-PhB(OxMe2)2ImMes'CH2}Rh(μ-H)(μ-Cl)Rh(η2-C8H14)2 (10) and {PhB(OxMe2)2ImMes}IrH(η3-C8H13) (11). In the former compound, a spontaneous oxidative addition of a mesityl ortho-methyl to give a mixed-valent dirhodium species is observed, while the iridium compound forms a monometallic allyl hydride. Photochemical reactions of dicarbonyl compounds 5 and 7 result in C–H bond oxidative addition providing the compounds {κ4-PhB(OxMe2)2ImMes'CH2}RhH(CO) (12) and {PhB(OxMe2)2ImMes}IrH(Ph)CO (13). In 12, oxidative addition results in cyclometalation of the mesityl ortho-methyl similar to 10, whereas the iridium compound reacts with the benzene solvent to give a rare crystallographically characterized cis

  19. Chemistry of Stable Carbenes and «Green» Technologies

    Directory of Open Access Journals (Sweden)

    Korotkikh, N.I.

    2015-11-01

    Full Text Available Brief analysis of fundamental research in the chemistry of stable carbenes and applications in the field of «green» chemistry on their basis carried out at the L.M. Litvinenko Institute of Physical Organic & Coal Chemistry of NAS of Ukraine over the last decade is given. Carbene versions of ester Claisen condensation to form zwitterionic compounds, the Leuckart-Wallach reaction with the autoreduction of carbenoid azolium salts, Hofmann cleavage of aminocarbene insertion products, an induced tandem autotransformation of 1,2,4-triazol-5-ylidenes into 5-amidino-1,2,4-triazoles were found. New carbene reactions of ad dition, deesterification, oxidation and complexation were revealed. Effective methods of obtaining stable carbenes and carbenoids were suggested. New types of carbenes, namely benzimidazolylidenes, superstable conjugated biscarbenes and new types of carbenoids were synthesized. The existence of hypernucleophilic carbenes was theoretically predicted and experimentally confirmed. The prospects of the use of carbenes and their derivatives, in particular, carbene complexes of transition metals in catalysis of organic reactions and the search of biologically active compounds were shown.

  20. The antimicrobial efficacy of sustained release silver–carbene complex-loaded l-tyrosine polyphosphate nanoparticles: Characterization, in vitro and in vivo studies

    Science.gov (United States)

    Hindi, Khadijah M.; Ditto, Andrew J.; Panzner, Matthew J.; Medvetz, Douglas A.; Han, Daniel S.; Hovis, Christine E.; Hilliard, Julia K.; Taylor, Jane B.; Yun, Yang H.; Cannon, Carolyn L.; Youngs, Wiley J.

    2009-01-01

    The pressing need to treat multi-drug resistant bacteria in the chronically infected lungs of cystic fibrosis (CF) patients has given rise to novel nebulized antimicrobials. We have synthesized a silver–carbene complex (SCC10) active against a variety of bacterial strains associated with CF and chronic lung infections. Our studies have demonstrated that SCC10-loaded into l-tyrosine polyphosphate nanoparticles (LTP NPs) exhibits excellent antimicrobial activity in vitro and in vivo against the CF relevant bacteria Pseudomonas aeruginosa. Encapsulation of SCC10 in LTP NPs provides sustained release of the antimicrobial over the course of several days translating into efficacious results in vivo with only two administered doses over a 72 h period. PMID:19395021

  1. Human colon cancer targeted pro-apoptotic, anti-metastatic and cytostatic effects of binuclear Silver(I)-N-Heterocyclic carbene (NHC) complexes.

    Science.gov (United States)

    Asif, Muhammad; Iqbal, Muhammad Adnan; Hussein, Mouayed A; Oon, Chern Ein; Haque, Rosenani A; Khadeer Ahamed, Mohamed B; Abdul Majid, Aman Shah; Abdul Majid, Amin Malik Shah

    2016-01-27

    The current mechanistic study was conducted to explore the effects of increased lipophilicity of binuclear silver(I)-NHC complexes on cytotoxicity. Two new silver(I)-N-Heterocyclic Carbene (NHC) complexes (3 and 4), having lypophilic terminal alkyl chains (Octyl and Decyl), were derived from meta-xylyl linked bis-benzimidazolium salts (1 and 2). Each of the synthesized compounds was characterized by microanalysis and spectroscopic techniques. The complexes were tested for their cytotoxicity against a panel of human cancer c as well normal cell lines using MTT assay. Based on MTT assay results, complex 4 was found to be selectively toxic towards human colorectal carcinoma cell line (HCT 116). Complex 4 was further studied in detail to explore the mechanism of cell death and findings of the study revealed that complex 4 has promising pro-apoptotic and anti-metastatic activities against HCT 116 cells. Furthermore, it showed pronounced cytostatic effects in HCT 116 multicellular spheroid model. Hence, binuclear silver(I)-NHC complexes with longer terminal aliphatic chains have worth to be further studied against human colon cancer for the purpose of drug development. Copyright © 2015 Elsevier Masson SAS. All rights reserved.

  2. Synthesis and characterization of nitrile functionalized silver(I)-N-heterocyclic carbene complexes: DNA binding, cleavage studies, antibacterial properties and mosquitocidal activity against the dengue vector, Aedes albopictus.

    Science.gov (United States)

    Asekunowo, Patrick O; Haque, Rosenani A; Razali, Mohd R; Avicor, Silas W; Wajidi, Mustafa F F

    2018-04-25

    A series of four benzimidazolium based nitrile-functionalized mononuclear-Ag(I)-N-heterocyclic carbene and binuclear-Ag(I)-N-heterocyclic carbene (Ag(I)-NHC) hexafluorophosphate complexes (5b-8b) were synthesized by reacting the corresponding hexafluorophosphate salts (1b-4b) with Ag 2 O in acetonitrile, respectively. These compounds were characterized by 1 H NMR, 13 C NMR, IR, UV-visible spectroscopic techniques, elemental analyses and molar conductivity. Additionally, 8b was structurally characterized by single crystal X-ray diffraction technique. Preliminary in vitro antibacterial evaluation was conducted for all the compounds against two standard bacteria; gram-positive (Staphylococcus aureus) and gram-negative (Escherichia coli) bacterial strains. Most of the Ag(I)-NHC complexes (5b-8b) showed moderate to good antibacterial activity with MIC values in the range of 12.5-100 μg/mL. Especially, compound 8b exhibited promising anti-Staphylococcus aureus activity with a low MIC value (12.5 μg/mL). However, all the hexafluorophosphate salts (1b-4b) were inactive against the bacteria strains. The preliminary interactive investigation revealed that the most active compound, 8b, could effectively intercalate into DNA to form 8b-DNA complex which shows a better binding ability for DNA (K b  = 3.627 × 10 6 ) than the complexes 5b-7b (2.177 × 10 6 , 8.672 × 10 5 and 6.665 × 10 5 , respectively). Nuclease activity of the complexes on plasmid DNA and Aedes albopictus genomic DNA was time-dependent, although minimal. The complexes were larvicidal to the mosquito, with 5b, 6b and 8b being highly active. Developmental progression from the larval to the adult stage was affected by the complexes, progressively being toxic to the insect's development with increasing concentration. These indicate the potential use of these complexes as control agents against bacteria and the dengue mosquito Ae. albopictus. Copyright © 2018 Elsevier Masson SAS. All

  3. Synthesis and Characterization of Chromium (III) Complexes with L-Glutamic Acid, Glycine and LCysteine

    OpenAIRE

    Kun Sri Budiasih; Chairil Anwar; Sri Juari Santosa; Hilda Ismail

    2013-01-01

    Some Chromium (III) complexes were synthesized with three amino acids: L Glutamic Acid, Glycine, and L-cysteine as the ligands, in order to provide a new supplement containing Cr(III) for patients with type 2 diabetes mellitus. The complexes have been prepared by refluxing a mixture of Chromium(III) chloride in aqueous solution with L-glutamic acid, Glycine, and L-cysteine after pH adjustment by sodium hydroxide. These complexes were characterized by Infrared and Uv-Vis s...

  4. Hydrogen Production and Storage on a Formic Acid/Bicarbonate Platform using Water-Soluble N-Heterocyclic Carbene Complexes of Late Transition Metals.

    Science.gov (United States)

    Jantke, Dominik; Pardatscher, Lorenz; Drees, Markus; Cokoja, Mirza; Herrmann, Wolfgang A; Kühn, Fritz E

    2016-10-06

    The synthesis and characterization of two water-soluble bis-N-heterocyclic carbene (NHC) complexes of rhodium and iridium is presented. Both compounds are active in H 2 generation from formic acid and in hydrogenation of bicarbonate to formate. The rhodium derivative is most active in both reactions, reaching a TOF of 39 000 h -1 and a TON of 449 000 for H 2 production. The catalytic hydrogenation reactions were carried out in an autoclave system and analyzed using the integrated peak areas in the 1 H NMR spectra. Decomposition of formic acid was investigated using a Fisher-Porter bottle equipped with a pressure transducer. Long-term stability for hydrogen evolution was tested by surveillance of the gas flow rate. The procedure does not require any additives like amines or inert gas conditions. Density functional theory calculations in agreement with experimental results suggest a bicarbonate reduction mechanism involving a second catalyst molecule, which provides an external hydride acting as reducing agent. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Molecular and electronic structure of chromium(V) nitrido complexes with azide and isothiocyanate ligands

    DEFF Research Database (Denmark)

    Bendix, Jesper; Birk, Torben; Weyhermüller, Thomas

    2005-01-01

    . This absorption provides the spectrochemical series for the equatorial ligands, which is found to be numerically almost identical to that determined for chromium(III). DFT calculations reproduce the observed structures and corroborate the ligand field picture of the electronic structure of these complexes....

  6. Thin films of molecular materials synthesized from fisher's carbene ferrocenyl: Film formation and electrical properties

    International Nuclear Information System (INIS)

    Sanchez-Vergara, M.E.; Ortiz, A.; Alvarez-Toledano, C.; Moreno, A.; Alvarez, J.R.

    2008-01-01

    The synthesis of materials from Fisher's carbene ferrocenyl of the elements chromium, molybdenum and tungsten was carried out. The Fisher's compounds that were synthesized included the following combinations of two different metallic atoms: iron with chromium, iron with molybdenum and iron with tungsten. The molecular solids' preparation was done in electro-synthesis cells with platinum electrodes. Thin films were prepared by vacuum thermal evaporation on quartz substrates and crystalline silicon wafers. Pellets and thin films from these compounds were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, energy-dispersive spectroscopy, atomic force microscopy and ellipsometry. The powder and thin films synthesized from these materials show the same intra-molecular bonds shown by infrared spectroscopy results, suggesting that thermal evaporation does not alter these bonds in spite of the thin films being amorphous, in contrast with other bimetallic complexes where material decomposition occurs. The differences in the conductivity values of the prepared films are very small, so they may be attributed to the different metallic ions employed in each case. The tungsten complex exhibits a higher conductivity than the molybdenum and chromium complexes at room temperature. Electrical conductivity values found for thin films are higher than for pellets made of the same molecular materials

  7. Enhanced sludge processing of HLW: Hydrothermal oxidation of chromium, technetium, and complexants by nitrate. 1998 annual progress report

    International Nuclear Information System (INIS)

    Buelow, S.J.; Robinson, J.M.

    1998-01-01

    'The objective of this project is to develop the scientific basis for hydrothermal separation of chromium from High Level Waste (HLW) sludges. The worked is aimed at attaining a fundamental understanding of chromium speciation, oxidation/reduction and dissolution kinetics, reaction mechanisms, and transport properties under hydrothermal conditions in both simple and complex salt solutions that will ultimately lead to an efficient chromium leaching process. This report summarizes the research over the first 1.5 years of a 3 year project. The authors have examined the dissolution of chromium hydroxide using different oxidants as a function of temperature and alkalinity. The results and possible applications to HLW sludges are discussed'

  8. Silver(I) complexes of mono- and bidentate N-heterocyclic carbene ligands: synthesis, crystal structures, and in vitro antibacterial and anticancer studies.

    Science.gov (United States)

    Haque, Rosenani A; Choo, Sze Yii; Budagumpi, Srinivasa; Iqbal, Muhammad Adnan; Al-Ashraf Abdullah, Amirul

    2015-01-27

    A series of benzimidazole-based N-heterocyclic carbene (NHC) proligands {1-benzyl-3-(2-methylbenzyl)-benzimidazolium bromide/hexafluorophosphate (1/4), 1,3-bis(2-methylbenzyl)-benzimidazolium bromide/hexafluorophosphate (2/5) and 1,3-bis(3-(2-methylbenzyl)-benzimidazolium-1-ylmethylbenzene dibromide/dihexafluorophosphate (3/6)} has been synthesized by the successive N-alkylation method. Ag complexes {1-benzyl-3-(2-methylbenzyl)-benzimidazol-2-ylidenesilver(I) hexafluorophosphate (7), 1,3-bis(2-methylbenzyl)-benzimidazol-2-ylidenesilver(I) hexafluorophosphate (8) and 1,3-bis(3-(2-methylbenzyl)-benzimidazol-2-ylidene)-1-ylmethylbenzene disilver(I) dihexafluorophosphate (9)} of NHC ligands have been synthesized by the treatment of benzimidazolium salts with Ag2O at mild reaction conditions. Both, NHC proligands and Ag-NHC complexes have been characterized by (1)H and (13)C{(1)H} NMR and FTIR spectroscopy and elemental analysis technique. Additionally, the structure of the NHC proligand 5 and the mononuclear Ag complexes 7 and 8 has been elucidated by the single crystal X-ray diffraction analysis. Both the complexes exhibit the same general structural motif with linear coordination geometry around the Ag centre having two NHC ligands. Preliminary in vitro antibacterial potentials of reported compounds against a Gram negative (Escherichia coli) and a Gram positive (Bacillus subtilis) bacteria evidenced the higher activity of mononuclear silver(I) complexes. The anticancer studies against the human derived colorectal cancer (HCT 116) and colorectal adenocarcinoma (HT29) cell lines using the MTT assay method, revealed the higher activity of Ag-NHC complexes. The benzimidazolium salts 4-6 and Ag-NHC complexes 7-9 displayed the following IC50 values against the HCT 116 and HT29 cell lines, respectively, 31.8 ± 1.9, 15.2 ± 1.5, 4.8 ± 0.6, 10.5 ± 1.0, 18.7 ± 1.6, 1.20 ± 0.3 and 245.0 ± 4.6, 8.7 ± 0.8, 146.1 ± 3.1, 7.6 ± 0.7, 5.5 ± 0.8, 103.0 ± 2.3 μM. Copyright

  9. Luminescent platinum(II) complexes with functionalized N-heterocyclic carbene or diphosphine selectively probe mismatched and abasic DNA

    OpenAIRE

    Che, CM; Chen, T; To, WP; Zou, T; FUNG, SK; Lok, CN; YANG, C; Cao, B

    2016-01-01

    The selective targeting of mismatched DNA overexpressed in cancer cells is an appealing strategy in designing cancer diagnosis and therapy protocols. Few luminescent probes that specifically detect intracellular mismatched DNA have been reported. Here we used Pt(II) complexes with luminescence sensitive to subtle changes in the local environment and report several Pt(II) complexes that selectively bind to and identify DNA mismatches. We evaluated the complexes' DNA-binding characteristics by ...

  10. Bicarbonate catalysis of exchange synthesis of [51Cr]Cr(III)-EDTA and other chromium complexes

    International Nuclear Information System (INIS)

    Aronson, F.L.; Strashun, A.M.; Lopez, C.; Steigman, J.

    1993-01-01

    Exchange syntheses of trivalent chromium complexes often require heating, thus limiting tagging of heat-sensitive biological compounds with 51 Cr. Bicarbonate at pH 6, accelerates the formation of mM Cr-EDTA. Accordingly, room temperature catalysis with [ 51 Cr]Cr(III) at 10 -7 -10 -8 M was investigated. Complexes were successfully formed with EDTA and iminodiacetic acid (electrophoretic analysis) and acetylacetone and tropolone (analyzed by chloroform extraction). The formation of these complexes normally requires extensive heating. (author)

  11. Synthesis and Characterization of Divalent Manganese, Iron, and Cobalt Complexes in Tripodal Phenolate/N-Heterocyclic Carbene Ligand Environments

    DEFF Research Database (Denmark)

    Käß, Martina; Hohenberger, Johannes; Adelhardt, Mario

    2014-01-01

    . The complete ligand series offers a convenient way of tuning the electronic and steric environment around the metal center, thus, allowing for control of the complex’s reactivity. This series of divalent complexes of Mn, Fe, and Co was synthesized and characterized by 1H NMR, IR, and UV/vis spectroscopy...... as well as by single-crystal X-ray diffraction studies. Variable-temperature SQUID magnetization measurements in the range from 2 to 300 K confirmed high-spin ground states for all divalent complexes and revealed a trend of increasing zero-field splitting |D| from Mn(II), to Fe(II), to Co(II) complexes...

  12. Enhanced sludge processing of HLW: Hydrothermal oxidation of chromium, technetium, and complexants by nitrate. 1997 mid-year progress report

    International Nuclear Information System (INIS)

    Buelow, S.

    1997-01-01

    'Treatment of High Level Waste (HLW) is the second most costly problem identified by OEM. In order to minimize costs of disposal, the volume of HLW requiring vitrification and long term storage must be reduced. Methods for efficient separation of chromium from waste sludges, such as the Hanford Tank Wastes (HTW), are key to achieving this goal since the allowed level of chromium in high level glass controls waste loading. At concentrations above 0.5 to 1.0 wt.% chromium prevents proper vitrification of the waste. Chromium in sludges most likely exists as extremely insoluble oxides and minerals, with chromium in the plus III oxidation state [1]. In order to solubilize and separate it from other sludge components, Cr(III) must be oxidized to the more soluble Cr(VI) state. Efficient separation of chromium from HLW could produce an estimated savings of $3.4B[2]. Additionally, the efficient separation of technetium [3], TRU, and other metals may require the reformulation of solids to free trapped species as well as the destruction of organic complexants. New chemical processes are needed to separate chromium and other metals from tank wastes. Ideally they should not utilize additional reagents which would increase waste volume or require subsequent removal. The goal of this project is to apply hydrothermal processing for enhanced chromium separation from HLW sludges. Initially, the authors seek to develop a fundamental understanding of chromium speciation, oxidation/reduction and dissolution kinetics, reaction mechanisms, and transport properties under hydrothermal conditions in both simple and complex salt solutions. The authors also wish to evaluate the potential of hydrothermal processing for enhanced separations of technetium and TRU by examining technetium and TRU speciation at hydrothermal conditions optimal for chromium dissolution.'

  13. Dehydrogenative Coupling of Primary Alcohols To Form Esters Catalyzed by a Ruthenium N-Heterocyclic Carbene Complex

    DEFF Research Database (Denmark)

    Sølvhøj, Amanda Birgitte; Madsen, Robert

    2011-01-01

    The ruthenium complex [RuCl2(IiPr)(p-cymene)] catalyzes the direct condensation of primary alcohols into esters and lactones with the release of hydrogen gas. The reaction is most effective with linear aliphatic alcohols and 1,4-diols and is believed to proceed with a ruthenium dihydride...

  14. Thin films of molecular materials synthesized from fisher's carbene ferrocenyl: Film formation and electrical properties

    Energy Technology Data Exchange (ETDEWEB)

    Sanchez-Vergara, M.E. [Coordinacion de Ingenieria Mecatronica. Escuela de Ingenieria, Universidad Anahuac del Norte. Avenida Lomas de la Anahuac s/n, Col. Lomas Anahuac, 52786, Huixquilucan (Mexico)], E-mail: elena.sanchez@anahuac.mx; Ortiz, A. [Instituto de Investigaciones en Materiales. Universidad Nacional Autonoma de Mexico. A. P. 70-360, 04510, Mexico, DF (Mexico); Alvarez-Toledano, C.; Moreno, A. [Instituto de Quimica, Universidad Nacional Autonoma de Mexico. Circuito Exterior, Ciudad Universitaria, 04510, Mexico, DF (Mexico); Alvarez, J.R. [Instituto Tecnologico y de Estudios Superiores de Monterrey, Campus Ciudad de Mexico. Calle del Puente 222, Col. Ejidos de Huipulco, 14380, Mexico, DF (Mexico)

    2008-07-31

    The synthesis of materials from Fisher's carbene ferrocenyl of the elements chromium, molybdenum and tungsten was carried out. The Fisher's compounds that were synthesized included the following combinations of two different metallic atoms: iron with chromium, iron with molybdenum and iron with tungsten. The molecular solids' preparation was done in electro-synthesis cells with platinum electrodes. Thin films were prepared by vacuum thermal evaporation on quartz substrates and crystalline silicon wafers. Pellets and thin films from these compounds were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, energy-dispersive spectroscopy, atomic force microscopy and ellipsometry. The powder and thin films synthesized from these materials show the same intra-molecular bonds shown by infrared spectroscopy results, suggesting that thermal evaporation does not alter these bonds in spite of the thin films being amorphous, in contrast with other bimetallic complexes where material decomposition occurs. The differences in the conductivity values of the prepared films are very small, so they may be attributed to the different metallic ions employed in each case. The tungsten complex exhibits a higher conductivity than the molybdenum and chromium complexes at room temperature. Electrical conductivity values found for thin films are higher than for pellets made of the same molecular materials.

  15. EPR investigation of the trivalent chromium complexes in SrTiO.sub.3./sub..

    Czech Academy of Sciences Publication Activity Database

    Azamat, Dmitry; Dejneka, Alexandr; Lančok, Ján; Jastrabík, Lubomír; Trepakov, Vladimír; Bryknar, Z.; Neverova, E.V.; Badalyan, A. G.

    2014-01-01

    Roč. 75, č. 2 (2014), s. 271-275 ISSN 0022-3697 R&D Projects: GA MŠk(CZ) LM2011029; GA TA ČR TA01010517; GA ČR GAP108/12/1941 Grant - others:SAFMAT(XE) CZ.2.16/3.1.00/22132 Institutional support: RVO:68378271 Keywords : electron paramagnetic resonance (EPR) * SrTiO 3 * chromium complexes Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.853, year: 2014

  16. H-D exchange in metal carbene complexes: Structure of cluster (μ-H)(μ-OCD3)Os3(CO)9{:C(CD3)NC2H8O}

    Science.gov (United States)

    Savkov, Boris; Maksakov, Vladimir; Kuratieva, Natalia

    2015-10-01

    X-ray and spectroscopic data for the new complex (μ-H)(μ-OCH3)Os3(CO)9{:C(CD3)NC2H8O} (2) obtained in the reaction of the (μ-H)(μ-Cl)Os3(CO)9{:C(CH3)NC2H8O} (1) with NaOCD3 in CD3OD solution are reported. It is shown that cluster 1 has the property of CH-acidity inherent of Fisher type carbenes. This had demonstrated using hydrogen deuterium exchange reaction in the presence of a strong base. Bridging chlorine to metoxide ligand substitution takes place during the reaction. The molecular structure of 2 is compared with known analogues.

  17. N-Heterocyclic Carbene Coinage Metal Complexes of the Germanium-Rich Metalloid Clusters [Ge9R3]− and [Ge9RI2]2− with R = Si(iPr3 and RI = Si(TMS3

    Directory of Open Access Journals (Sweden)

    Felix S. Geitner

    2017-07-01

    Full Text Available We report on the synthesis of novel coinage metal NHC (N-heterocyclic carbene compounds of the germanium-rich metalloid clusters [Ge9R3]− and [Ge9RI2]2− with R = Si(iPr3 and RI = Si(TMS3. NHCDippCu{η3Ge9R3} with R = Si(iPr3 (1 represents a less bulky silyl group-substituted derivative of the known analogous compounds with R = Si(iBu3 or Si(TMS3. The coordination of the [NHCDippCu]+ moiety to the cluster unit occurs via one triangular face of the tri-capped trigonal prismatic [Ge9] cluster. Furthermore, a series of novel Zintl cluster coinage metal NHC compounds of the type (NHCM2{η3Ge9RI2} (RI = Si(TMS3 M = Cu, Ag and Au; NHC = NHCDipp or NHCMes is presented. These novel compounds represent a new class of neutral dinuclear Zintl cluster coinage metal NHC compounds, which are obtained either by the stepwise reaction of a suspension of K12Ge17 with Si(TMS3Cl and the coinage metal carbene complexes NHCMCl (M = Cu, Ag, Au, or via a homogenous reaction using the preformed bis-silylated cluster K2[Ge9(Si(TMS32] and the corresponding NHCMCl (M = Cu, Ag, Au complex. The molecular structures of NHCDippCu{η3Ge9(Si(iPr33} (1 and (NHCDippCu2{η3-Ge9(Si(TMS32} (2 were determined by single crystal X-ray diffraction methods. In 2, the coordination of the [NHCDippCu]+ moieties to the cluster unit takes place via both open triangular faces of the [Ge9] entity. Furthermore, all compounds were characterized by means of NMR spectroscopy (1H, 13C, 29Si and ESI-MS.

  18. Grafted chromium 13-membered dioxo-macrocyclic complex into aminopropyl-based nanoporous SBA-15

    Energy Technology Data Exchange (ETDEWEB)

    Tarlani, Aliakbar, E-mail: Tarlani@ccerci.ac.ir [Inorganic Nanostructures and Catalysts Research Laboratory, Chemistry and Chemical Engineering Research Center of Iran, Pajoohesh Boulevard, km 17, Karaj Highway, Tehran 14968-13151 (Iran, Islamic Republic of); Joharian, Monika; Narimani, Khashayar [Inorganic Nanostructures and Catalysts Research Laboratory, Chemistry and Chemical Engineering Research Center of Iran, Pajoohesh Boulevard, km 17, Karaj Highway, Tehran 14968-13151 (Iran, Islamic Republic of); Muzart, Jacques [Institut de Chimie Moléculaire de Reims, CNRS-Université de Reims Champagne-Ardenne, BP 1039, 51687 Reims Cedex 2 (France); Fallah, Mahtab [Inorganic Nanostructures and Catalysts Research Laboratory, Chemistry and Chemical Engineering Research Center of Iran, Pajoohesh Boulevard, km 17, Karaj Highway, Tehran 14968-13151 (Iran, Islamic Republic of)

    2013-07-15

    In a new approach, chromium (III) tetraaza dioxo ligand was grafted onto functionalized SBA-15 after four step reactions by using coordinating ability of anchored amino functionalized SBA-15. After the termination of each step, the obtained product was characterized by FT-IR, low-angle X-ray diffraction (LA-XRD), N{sub 2} adsorption–desorption isotherms (Brunauer–Emmett–Teller (BET)–Barret–Joyner–Halenda (BJH)) and thermogravimetric analysis (TGA), and used as catalyst for the efficient and regioselective alcoholysis of styrene oxide to 2-alkoxy-1-phenylethanol product at ambient temperature. - Graphical abstract: Chromium (III) tetraaza dioxo ligand was grafted onto functionalized SBA-15 using coordinating ability of anchored amino functionalized SBA-15. Preparation of the catalyst is depicted in Scheme 1. - Highlights: • Dioxo tetraazachromium macrocyclic complex grafted into the SBA-15-NH{sub 2} channels. • The bond is created by coordinating ability of anchored amino functionalized SBA-15. • The prepared nanocatalyst has superior activity in the alcoholysis of styrene oxide. • The catalyst is reusable at ambient temperature for the mentioned reaction.

  19. Unexpected rearrangements in the synthesis of an unsymmetrical tridentate dianionic N-heterocyclic carbene

    KAUST Repository

    Despagnet-Ayoub, Emmanuelle; Miqueu, Karinne; Sotiropoulos, Jean-Marc; Henling, Lawrence M.; Day, Michael W.; Labinger, Jay A.; Bercaw, John E.

    2013-01-01

    Starting from the same ethylenediamine species, three valuable carbene precursors were synthesized under differing conditions: a tridentate dianionic N-heterocyclic carbene bearing an aniline, a phenol and a central dihydroimidazolium salt, its benzimidazolium isomer by intramolecular rearrangement and a dicationic benzimidazolium-benzoxazolium salt by changing the Brønsted acid from HCl to HBF4. A DFT study was performed to understand the rearrangement pathway. The structure of a bis[(NCO)carbene] zirconium complex was determined. © 2013 The Royal Society of Chemistry.

  20. Ethylene polymerization by PN3-type pincer chromium(III) complexes

    KAUST Repository

    Gong, Dirong; Liu, Wen; Chen, Tao; Chen, Zhongren; Huang, Kuo-Wei

    2014-01-01

    Chromium (III) complexes, Cr1, [2,6-(tBu2PNH) 2C5H4N]CrCl3; Cr2, [2,6-(Ph 2PNH)2C5H4N]CrCl3; Cr3, [2-(tBu2PNH)C5H4N]CrCl3 THF; Cr4, [6-(tBu2PNH)C5H4N-2- CH2NEt2]CrCl3; Cr5, [6-(tBu 2PNH)C5H4N-2-C3H2N 2]CrCl3; Cr6, [6-(tBu2PNH)C 5H4N-2-(3,5-Me2)C3H 2

  1. Photocatalytic Reduction of Hexavalent Chromium Induced by Photolysis of Ferric/tartrate Complex

    Energy Technology Data Exchange (ETDEWEB)

    Feng, Xianghua; Ding, Shimin; Zhang, Lixian [Yangtze Normal Univ., Fuling (China)

    2012-11-15

    Photocatalytic reduction of hexavalent chromium (Cr(VI)) in ferric-tartrate system under irradiation of visible light was investigated. Effects of light resources, initial pH value and initial concentration of various reactants on Cr(VI) photocatalytic reduction were studied. Photoreaction kinetics was discussed and a possible photochemical pathway was proposed. The results indicate that Fe(III)-tartrate system is able to rapidly and effectively photocatalytically reduce Cr(VI) utilizing visible light. Initial pH variations results in the concentration changes of Fe(III)-tartrate complex in this system, and pH at 3.0 is optimal for Cr(VI) photocatalytic reduction. Efficiency of Cr(VI) photocatalytic reduction increases with increasing initial concentrations of Cr(VI), Fe(III) and tartrate. Kinetics analysis indicates that initial Fe(III) concentration affects Cr(VI) photoreduction most significantly.

  2. Photocatalytic Reduction of Hexavalent Chromium Induced by Photolysis of Ferric/tartrate Complex

    International Nuclear Information System (INIS)

    Feng, Xianghua; Ding, Shimin; Zhang, Lixian

    2012-01-01

    Photocatalytic reduction of hexavalent chromium (Cr(VI)) in ferric-tartrate system under irradiation of visible light was investigated. Effects of light resources, initial pH value and initial concentration of various reactants on Cr(VI) photocatalytic reduction were studied. Photoreaction kinetics was discussed and a possible photochemical pathway was proposed. The results indicate that Fe(III)-tartrate system is able to rapidly and effectively photocatalytically reduce Cr(VI) utilizing visible light. Initial pH variations results in the concentration changes of Fe(III)-tartrate complex in this system, and pH at 3.0 is optimal for Cr(VI) photocatalytic reduction. Efficiency of Cr(VI) photocatalytic reduction increases with increasing initial concentrations of Cr(VI), Fe(III) and tartrate. Kinetics analysis indicates that initial Fe(III) concentration affects Cr(VI) photoreduction most significantly

  3. Synthesis and Characterization of Hexahapto-Chromium Complexes of Single-Walled Carbon Nanotubes

    KAUST Repository

    Kalinina, Irina

    2016-12-17

    This chapter employs purified pristine single-walled carbon nanotubes (SWNTs) and octadecylaminefunctionalized-SWNTs. These SWNTs are employed for investigate the potential of the SWNT sidewall to function as a hexahapto ligand for chromium (Cr), with in-depth characterization of the products using some of the techniques, such as thermogravimetric analysis (TGA), transmission electron microscopy (TEM), x-ray photoelectron spectroscopy (XPS). Purified electric arc (EA)-produced SWNTs (P2-SWNT) and octadecylaminefunctionalized SWNTs were obtained from Carbon Solutions, Inc. The TEM images show the removal of the Cr particles from the outer surface of the SWNT bundles in the SWNT-Cr complexes after decomplexation; Cr attachment to the surface of the as-prepared complexes (η6-SWNT)Cr(CO)3 and (η6-SWNT-CONH(CH2)17CH3)Cr(CO)3 is clearly evident. The positions of the bands in the Raman spectra of SWNTs are sensitive to doping and thus the chapter examines the effect of complexation of the Cr(CO)3 and Cr(η6-benzene) units on the position of the G and 2D bands in the (η6-SWNT)Cr(CO)3 and (η6-SWNT)Cr(η6-benzene) complexes.

  4. Magnetic properties of 1 : 4 complexes of CoCl2 and pyridines carrying carbenes (S(0) = 4/2, 6/2, and 8/2) in diluted frozen solution; influence of carbene multiplicity on heterospin single-molecule magnets.

    Science.gov (United States)

    Karasawa, Satoru; Nakano, Kimihiro; Tanokashira, Jun-ichi; Yamamoto, Noriko; Yoshizaki, Takahito; Koga, Noboru

    2012-11-28

    The microcrystalline sample of a parent complex, [CoCl(2)(py)(4)], showed a single-molecule magnet (SMM) behavior with an effective activation barrier, U(eff)/k(B), of 16 K for reversal of the magnetism in the presence of a dc field of 3 kOe. Pyridine ligands having 2-4 diazo moieties, DYpy; Y = 2, 3l, 3b, and 4, were prepared and confirmed to be quintet, septet, septet, and nonet in the ground state, respectively, after irradiation. The 1 : 4 complexes, CoCl(2)(DYpy)(4); Y = 2, 3l, 3b, and 4 in frozen solutions after irradiation showed the magnetic behaviors of SMMs with total spin multiplicity, S(total) = 17/2, 25/2, 25/2, and 33/2, respectively. Hysteresis loops depending on the temperature were observed and the values of coercive force, H(c), at 1.9 K were 12, 8.4, 11, and 8.1 kOe for CoCl(2)(CYpy)(4); Y = 2, 3l, 3b, and 4, respectively. In dynamic magnetic susceptibility experiments, ac magnetic susceptibility data obeyed the Arrhenius law to give U(eff)/k(B) values of 94, 92, 93, and 87 K for CoCl(2)(CYpy)(4); Y = 2, 3l, 3b, and 4, respectively, while the relaxation times for CoCl(2)(CYpy)(4); Y = 2 and 3l, obtained by dc magnetization decay in the range of 3.5-1.9 K slightly deviated downward from Arrhenius plots on cooling. The dynamic magnetic behaviors for CoCl(2)(CYpy)(4) including [CoCl(2)(py)(4)] and CoCl(2)(C1py)(4) suggested that the generated carbenes interacted with the cobalt ion to increase the relaxation time, τ(q), due to the spin quantum tunneling magnetization, which became larger with increasing S(total) of the complex.

  5. Experimental and theoretical investigations on the high-electron donor character of pyrido-annelated N-heterocyclic carbenes

    Directory of Open Access Journals (Sweden)

    Michael Nonnenmacher

    2016-08-01

    Full Text Available Rh(CO2Cl(NHC complexes of dipyrido-annelated N-heterocyclic carbenes were prepared. From the C–H coupling constant of the respective imidazolium salts and the N–C–N angle of the N-heterocyclic carbene (NHC, a weaker σ-donor character than that of typical unsaturated NHCs is expected. However, the IR stretching frequencies of their Rh(CO2Cl complexes suggest an electron-donor character even stronger than that of saturated NHCs. We ascribe this to the extremely weak π-acceptor character of the dipyrido-annelated NHCs caused by the conjugated 14 πe− system that thus allows for an enhanced Rh–CO backbonding. This extremely low π-acceptor ability is also corroborated by the 77Se NMR chemical shift of −55.8 ppm for the respective selenourea, the lowest value ever measured for imidazole derived selenoureas. DFT-calculations of the free carbene confirm the low σ-donor character by the fact that the σ-orbital of the carbene is the HOMO−1 that lies 0.58 eV below the HOMO which is located at the π-system. Natural population analysis reveals the lowest occupation of the pπ-orbital for the saturated carbene carbon atom and the highest for the pyrido-annelated carbene. Going from the free carbene to the Rh(CO2Cl(NHC complexes, the increase in occupancy of the complete π-system of the carbene ligand upon coordination is lowest for the pyrido-annelated carbene and highest for the saturated carbene.

  6. Alkali metal cation complexation and solvent interactions by robust chromium(III) fluoride complexes

    DEFF Research Database (Denmark)

    Birk, T.; Magnussen, M.J.; Piligkos, Stergios

    2010-01-01

    )] have been synthesized from mer-[CrF3(py)(3)] and shown to precipitate sodium salts from solution, of which 3[CrF3(Me(3-)tacn)]center dot 2Na(Bph(4)).solv and 6[CrF3(terpy)]center dot 4Na(Bph(4)).solv have been crystallographically characterized. In these clusters, the neutral fluoride complexes bring...

  7. [Cr(N)(acac)2]: A simple chromium nitride complex and its reactivity towards late transition metals

    DEFF Research Database (Denmark)

    Hedegaard, Erik Donovan; Schau-Magnussen, Magnus; Bendix, Jesper

    2011-01-01

    A new simple chromium(V) nitride complex, Cr(N)(acac)2 (1) has been prepared by nitrogen atom transfer. X-ray crystallography shows a short Cr-N bond at 1.5564(11) Å and equatorial Cr-O distances in the range 1.9387(9) – 1.9485(9) Å. 1 reacts as a p-backbonding ligand ......A new simple chromium(V) nitride complex, Cr(N)(acac)2 (1) has been prepared by nitrogen atom transfer. X-ray crystallography shows a short Cr-N bond at 1.5564(11) Å and equatorial Cr-O distances in the range 1.9387(9) – 1.9485(9) Å. 1 reacts as a p-backbonding ligand ...

  8. Ethylene polymerization by PN3-type pincer chromium(III) complexes

    KAUST Repository

    Gong, Dirong

    2014-12-01

    Chromium (III) complexes, Cr1, [2,6-(tBu2PNH) 2C5H4N]CrCl3; Cr2, [2,6-(Ph 2PNH)2C5H4N]CrCl3; Cr3, [2-(tBu2PNH)C5H4N]CrCl3 THF; Cr4, [6-(tBu2PNH)C5H4N-2- CH2NEt2]CrCl3; Cr5, [6-(tBu 2PNH)C5H4N-2-C3H2N 2]CrCl3; Cr6, [6-(tBu2PNH)C 5H4N-2-(3,5-Me2)C3H 2N2]CrCl3; Cr7, [6-(tBu 2PNH)C5H4N-2-(3,5-iPr 2)C3H2N2]CrCl3; Cr8, [6-(tBu2PNH)C5H4N-2-(3,5-Ph 2)C3H2N2]CrCl3, bearing a family of neutral PN3-type pincer ligands have been prepared. The molecular structure of Cr2 was further elucidated by the X-ray crystallographic analysis, showing an octahedral geometry. Treatment of these complexes with MAO or alkylaluminum led to catalysts with moderate activities (about 105 g (PE)/Cr(mol) h) for ethylene polymerization, affording exclusively linear low molecular weight solid PE without any detectable oligomers. Among Cr1-Cr8, the highest activity was achieved for Cr1/MAO at room temperature with production of PE with highest molecular weight, indicating that replacement of both tBu groups in Cr1 with Ph groups, or one PtBu2 with the N (imine) arm, resulted in a lower catalytic activity and lower M w. © 2014 Elsevier B.V.

  9. N-Heterocyclic carbene functionalized goup 7-9 transition metal

    NARCIS (Netherlands)

    Aktas, H.; Slootweg, J.C.; Ehlers, A.W.; Lutz, M.; Spek, A.L.; Lammertsma, K.

    2009-01-01

    The N-heterocyclic carbene (NHC) functionalized phosphinidene complexes [(pCy)(IiPr2Me2)- RudPMes*] (4), [(pCy)(IiPr2Me2)OsdPMes*] (6), and [(Cp*)(IiPr2Me2)RhdPMes*] (7) were generated by a double-dehydrohalogenation-ligation sequence of the corresponding primary phosphine complexes with 3 equiv of

  10. Stereoselective 1,3-Insertions of Rhodium(II) Azavinyl Carbenes

    Science.gov (United States)

    Chuprakov, Stepan; Worrell, Brady T.; Selander, Nicklas; Sit, Rakesh K.; Fokin, Valery V.

    2014-01-01

    Rhodium(II) azavinyl carbenes, conveniently generated from 1-sulfonyl-1,2,3-triazoles, undergo a facile, mild and convergent formal 1,3-insertion into N–H and O–H bonds of primary and secondary amides, various alcohols, and carboxylic acids to afford a wide range of vicinally bis-functionalized Z-olefins with perfect regio- and stereoselectively. Utilizing the distinctive functionality installed through these reactions, a number of subsequent rearrangements and cyclizations expand the repertoire of valuable organic building blocks constructed by reactions of transition metal carbene complexes, including α-allenyl ketones and amino-substituted heterocycles. PMID:24295389

  11. Extraction of bivalent vanadium as its pyridine thiocyanate complex and separation from uranium, titanium, chromium and aluminium

    International Nuclear Information System (INIS)

    Yatirajam, V.; Arya, S.P.

    1975-01-01

    A simple method is described for the extraction of V(II) as its pyridine thiocyanate complex. Vanadate is reduced to V(II) in 1 to 2 N sulphuric acid by zinc amalgam. Thiocyanate and pyridine are added, the solution is adjusted to pH 5.2 to 5.5 and the complex extracted with chloroform. The vanadium is back-extracted with peroxide solution. Zinc from the reductant accompanies the vanadium but alkali and alkaline earth metal ions, titanium, uranium, chromium and aluminium are separated, besides those ions reduced to the elements by zinc amalgam. The method takes about 20 min and is applicable to microgram as well as milligram amounts of vanadium. (author)

  12. Pincer-CNC mononuclear, dinuclear and heterodinuclear Au(III) and Pt(II) complexes supported by mono- and poly-N-heterocyclic carbenes: synthesis and photophysical properties.

    Science.gov (United States)

    Gonell, S; Poyatos, M; Peris, E

    2016-04-07

    A family of cyclometallated Au(iii) and Pt(ii) complexes containing a CNC-pincer ligand (CNC = 2,6-diphenylpyridine) supported by pyrene-based mono- or bis-NHC ligands have been synthesized and characterized, together with the preparation of a Pt-Au hetero-dimetallic complex based on a Y-shaped tris-NHC ligand. The photophysical properties of all the new species and of two related Ru(ii)-arene complexes were studied and compared. Whereas the pyrene-based complexes only exhibit emission in solution, those containing the Y-shaped tris-NHC ligand are only luminescent when dispersed in poly(methyl methacrylate) (PMMA). In particular, the pyrene-based complexes were found to be emissive in the range of 373-440 nm, with quantum yields ranging from 3.1 to 6.3%, and their emission spectra were found to be almost superimposable, pointing to the fluorescent pyrene-centered nature of the emission. This observation suggests that the emission properties of the pyrene fragment may be combined with some of the numerous applications of NHCs as supporting ligands allowing, for instance, the design of biological luminescent agents.

  13. Adjusting the DNA Interaction and Anticancer Activity of Pt(II) N-Heterocyclic Carbene Complexes by Steric Shielding of the Trans Leaving Group

    Czech Academy of Sciences Publication Activity Database

    Muenzner, J.K.; Rehm, T.; Biersack, B.; Casini, A.; de Graaf, I.; Worawutputtapong, P.; Noor, A.; Kempe, R.; Brabec, Viktor; Kašpárková, Jana; Schobert, R.

    2015-01-01

    Roč. 58, č. 15 (2015), s. 6283-6292 ISSN 0022-2623 R&D Projects: GA ČR(CZ) GA14-21053S Institutional support: RVO:68081707 Keywords : PLATINUM COMPLEXES * CANCER-CELLS * CISPLATIN Subject RIV: BO - Biophysics Impact factor: 5.589, year: 2015

  14. N-heterocyclic carbene copper(I) catalysed N-methylation of amines using CO2

    KAUST Repository

    Santoro, Orlando

    2015-09-30

    The N-methylation of amines using CO2 and PhSiH3 as source of CH3 was efficiently performed using a N-heterocyclic carbene copper(I) complex. The methodology was found compatible with aromatic and aliphatic primary and secondary amines. Synthetic and computational studies have been carried out to support the proposed reaction mechanism for this transformation.

  15. N-heterocyclic carbene copper(I) catalysed N-methylation of amines using CO2

    KAUST Repository

    Santoro, Orlando; Lazreg, Faï ma; Minenkov, Yury; Cavallo, Luigi; Cazin, Catherine S. J.

    2015-01-01

    The N-methylation of amines using CO2 and PhSiH3 as source of CH3 was efficiently performed using a N-heterocyclic carbene copper(I) complex. The methodology was found compatible with aromatic and aliphatic primary and secondary amines. Synthetic and computational studies have been carried out to support the proposed reaction mechanism for this transformation.

  16. Alkyne hydroarylation with Au N-heterocyclic carbene catalysts

    Directory of Open Access Journals (Sweden)

    Cristina Tubaro

    2013-02-01

    Full Text Available Mono- and dinuclear gold complexes with N-heterocyclic carbene (NHC ligands have been employed as catalysts in the intermolecular hydroarylation of alkynes with simple unfunctionalised arenes. Both mono- and dinuclear gold(III complexes were able to catalyze the reaction; however, the best results were obtained with the mononuclear gold(I complex IPrAuCl. This complex, activated with one equivalent of silver tetrafluoroborate, exhibited under acidic conditions at room temperature much higher catalytic activity and selectivity compared to more commonly employed palladium(II catalysts. Moreover, the complex was active, albeit to a minor extent, even under neutral conditions, and exhibited lower activity but higher selectivity compared to the previously published complex AuCl(PPh3. Preliminary results on intramolecular hydroarylations using this catalytic system indicate, however, that alkyne hydration by traces of water may become a serious competing reaction.

  17. Effects of an amylopectin and chromium complex on the anabolic response to a suboptimal dose of whey protein.

    Science.gov (United States)

    Ziegenfuss, T N; Lopez, H L; Kedia, A; Habowski, S M; Sandrock, J E; Raub, B; Kerksick, C M; Ferrando, A A

    2017-01-01

    Previous research has demonstrated the permissive effect of insulin on muscle protein kinetics, and the enhanced insulin sensitizing effect of chromium. In the presence of adequate whole protein and/or essential amino acids (EAA), insulin has a stimulatory effect on muscle protein synthesis, whereas in conditions of lower blood EAA concentrations, insulin has an inhibitory effect on protein breakdown. In this study, we determined the effect of an amylopectin/chromium (ACr) complex on changes in plasma concentrations of EAA, insulin, glucose, and the fractional rate of muscle protein synthesis (FSR). Using a double-blind, cross-over design, ten subjects (six men, four women) consumed 6 g whey protein + 2 g of the amylopectin-chromium complex (WPACr) or 6 g whey protein (WP) after an overnight fast. FSR was measured using a primed, continuous infusion of ring-d 5 -phenylalanine with serial muscle biopsies performed at 2, 4, and 8 h. Plasma EAA and insulin were assayed by ion-exchange chromatography and ELISA, respectively. After the biopsy at 4 h, subjects ingested their respective supplement, completed eight sets of bilateral isotonic leg extensions at 80% of their estimated 1-RM, and a final biopsy was obtained 4 h later. Both trials increased EAA similarly, with peak levels noted 30 min after ingestion. Insulin tended ( p  = 0.09) to be higher in the WPACr trial. Paired samples t-tests using baseline and 4-h post-ingestion FSR data separately for each group revealed significant increases in the WPACr group (+0.0197%/h, p  = 0.0004) and no difference in the WP group (+0.01215%/hr, p  = 0.23). Independent t-tests confirmed significant ( p  = 0.045) differences in post-treatment FSR between trials. These data indicate that the addition of ACr to a 6 g dose of whey protein (WPACr) increases the FSR response beyond what is seen with a suboptimal dose of whey protein alone.

  18. Formation of methane versus benzene in the reactions of (C{sub 5}Me{sub 5}){sub 2}Th(CH{sub 3}){sub 2} with [CH{sub 3}PPh{sub 3}]X (X=Cl, Br, I) yielding thorium-carbene or thorium-ylide complexes

    Energy Technology Data Exchange (ETDEWEB)

    Rungthanaphatsophon, Pokpong; Behrle, Andrew C.; Barnes, Charles L.; Walensky, Justin R. [Department of Chemistry, University of Missouri, Columbia, MO (United States); Bathelier, Adrien; Castro, Ludovic; Maron, Laurent [Toulouse Univ. and CNRS, INSA, UPS, CNRS, UMR, UMR 5215, LPCNO (France)

    2017-10-09

    The reaction of (C{sub 5}Me{sub 5}){sub 2}Th(CH{sub 3}){sub 2} with the phosphonium salts [CH{sub 3}PPh{sub 3}]X (X=Cl, Br, I) was investigated. When X=Br and I, two equivalents of methane are liberated to afford (C{sub 5}Me{sub 5}){sub 2}Th[CHPPh{sub 3}]X, rare terminal phosphorano-stabilized carbenes with thorium. These complexes feature the shortest thorium-carbon bonds (∼2.30 Aa) reported to date, and electronic structure calculations show some degree of multiple bonding. However, when X=Cl, only one equivalent of methane is lost with concomitant formation of benzene from an unstable phosphorus(V) intermediate, yielding (C{sub 5}Me{sub 5}){sub 2}Th[κ{sup 2}-(C,C{sup '})-(CH{sub 2})(CH{sub 2})PPh{sub 2}]Cl. Density functional theory (DFT) investigations of the reaction energy profiles for [CH{sub 3}PPh{sub 3}]X, X=Cl and I showed that in the case of iodide, thermodynamics prevents the production of benzene and favors formation of the carbene. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  19. A theobromine derived silver N-heterocyclic carbene: synthesis, characterization, and antimicrobial efficacy studies on cystic fibrosis relevant pathogens.

    Science.gov (United States)

    Panzner, Matthew J; Hindi, Khadijah M; Wright, Brian D; Taylor, Jane B; Han, Daniel S; Youngs, Wiley J; Cannon, Carolyn L

    2009-09-21

    The increasing incidence of multidrug-resistant (MDR) pulmonary infections in the cystic fibrosis (CF) population has prompted the investigation of innovative silver based therapeutics. The functionalization of the naturally occurring xanthine theobromine at the N(1) nitrogen atom with an ethanol substituent followed by the methylation of the N(9) nitrogen atom gives the N-heterocyclic carbene precursor 1-(2-hydroxyethyl)-3,7,9-trimethylxanthinium iodide. The reaction of this xanthinium salt with silver acetate produces the highly hydrophilic silver carbene complex SCC8. The in vitro antimicrobial efficacy of this newly synthesized complex was evaluated with excellent results on a variety of virulent and MDR pathogens isolated from CF patients. A comparative in vivo study between the known caffeine derived silver carbene SCC1 and SCC8 demonstrated the ability of both complexes to improve the survival rates of mice in a pneumonia model utilizing the clinically isolated infectious strain of Pseudomonas aeruginosa PA M57-15.

  20. (VI) ML6 Complexes

    African Journals Online (AJOL)

    A geometric analysis revealed that beta-(C-H) and alpha-(C-C) can occupy the seventh and eighth coordination sites in the title Fischer carbene complexes as agostic interactions, which allows classifying the carbene as a η3 ligand in these cases. This theory was supported by the relative energies of the conformers and an ...

  1. Final Report - Elucidating Bioreductive Transformations within Physically Complex Media: Impact on the Fate and Transport of Uranium and Chromium

    International Nuclear Information System (INIS)

    Benner, Shawn G.; Fendorf, Scott

    2009-01-01

    In situ stabilization (inclusive of natural attenuation) of toxic metals and radionuclides is an attractive approach for remediating many contaminated DOE sites. By immobilizing toxic metals and radionuclides in place, the removal of contaminated water to the surface for treatment as well as the associated disposal costs are avoided. To enhance in situ remediaton, microbiological reductive stabilization of contaminant metals has been, and continues to be, actively explored. It is likely that surface and subsurface microbial activity can alter the redox state of toxic metals and radionuclides, either directly or indirectly, so they are rendered immobile. Furthermore, anaerobic bacterial metabolic products will help to buffer pulses of oxidation, typically from fluxes of nitrate or molecular oxygen, and thus may stabilize reduced contaminants from oxidative mobilization. Uranium and chromium are two elements of particular concern within the DOE complex that, owing to their abundance and toxicity, appear well suited for biologically mediated reductive stabilization. Subsurface microbial activity can alter the redox state of toxic metals and radionuclides, rending them immobile. Imparting an important criterion on the probability that contaminants will undergo reductive stabilization, however, is the chemical and physical heterogeneity of the media. Our research first examined microbially induced transformation of iron (hydr)oxide minerals and their impact on contaminant attenuation. We revealed that in intricate cascade of geochemical reactions is induced by microbially produced Fe(II), and that during transformation contaminants such as U(VI) can be incorporated into the structure, and a set of Fe(II) bearing solids capable of reducing Cr(VI) and stabilizing resulting Cr(III). We also note, however, that common subsurface constituents such as phosphate can modify iron oxide transformation pathways and thus impact contaminant sequestration - 'affecting both Cr and U

  2. Elucidating Bioreductive Transformations within Physically Complex Media: Impact on the Fate and Transport of Uranium and Chromium

    International Nuclear Information System (INIS)

    Fendorf, Scott; Francis, Chris; Jardine, Phil; Benner, Shawn

    2009-01-01

    In situ stabilization (inclusive of natural attenuation) of toxic metals and radionuclides is an attractive approach for remediating many contaminated DOE sites. By immobilizing toxic metals and radionuclides in place, the removal of contaminated water to the surface for treatment as well as the associated disposal costs are avoided. To enhance in situ remediaton, microbiological reductive stabilization of contaminant metals has been, and continues to be, actively explored. It is likely that surface and subsurface microbial activity can alter the redox state of toxic metals and radionuclides, either directly or indirectly, so they are rendered immobile. Furthermore, anaerobic bacterial metabolic products will help to buffer pulses of oxidation, typically from fluxes of nitrate or molecular oxygen, and thus may stabilize reduced contaminants from oxidative mobilization. Uranium and chromium are two elements of particular concern within the DOE complex that, owing to their abundance and toxicity, appear well suited for biologically mediated reductive stabilization. Subsurface microbial activity can alter the redox state of toxic metals and radionuclides, rending them immobile. Imparting an important criterion on the probability that contaminants will undergo reductive stabilization, however, is the chemical and physical heterogeneity of the media. Our research first examined microbially induced transformation of iron (hydr)oxide minerals and their impact on contaminant attenuation. We revealed that in intricate cascade of geochemical reactions is induced by microbially produced Fe(II), and that during transformation contaminants such as U(VI) can be incorporated into the structure, and a set of Fe(II) bearing solids capable of reducing Cr(VI) and stabilizing resulting Cr(III). We also note, however, that common subsurface constituents such as phosphate can modify iron oxide transformation pathways and thus impact contaminant sequestration - affecting both Cr and U

  3. Studies of coal structure using carbene chemistry

    Energy Technology Data Exchange (ETDEWEB)

    1990-01-01

    The object of this grant was to react coal, derivatized forms of coal, and solvent swelled coal with carbenes (divalent carbon species) under mild conditions. These carbenes were to be prepared by treating the coal with several diazo compounds and then thermally decomposing them at relatively low temperatures (80--130{degree}C). The carbenes were to be chosen to show varying selectively toward aromatic rings containing heteroatom functionalities and toward polynuclear aromatic systems. In some instances, where selectivities toward aromatic and heteroaromatic ring systems were not known, model studies were to be carried out. Because of the generally mild conditions employed and the good selectivity anticipated, and actually observed with one particular system, it was expected that this methodology would provide structural information about the coal, along with data on the extent of occurrence and type of aromatic systems. After carbene reactions, treatment of the coal samples was to include extractions and thermolysis. Physical studies included thermogravimetric analysis, diffuse reflectance FT-IR spectroscopy, NMR ({sup 1}H and {sup 13}C) spectroscopy, gas chromatography, GC/MS and GC/FT-IR. 7 figs., 10 tabs.

  4. Trans-1,4 selective polymerization of 1,3-butadiene with symmetry pincer chromium complexes activated by MMAO

    KAUST Repository

    Gong, Dirong; Jia, Xiaoyu; Wang, Baolin; Zhang, Xuequan; Huang, Kuo-Wei

    2014-01-01

    Tridentate chromium complexes (Cr1-Cr7) incorporated with symmetrical pincer ligand bis(arylimino)pyridine and bis(pyrzaolyl)pyridine have been synthesized and characterized by elemental analyis, FT-IR as well as ESI-MS. X-ray diffraction reveals solids-state structures of Cr2, Cr4 and Cr6 all adopt pseudo-octahedral coordination environment with respect to metal center. All complexes have been tested in stereoregulated polymerization of butadiene under various polymerization conditions. The trans-1,4 and cis-1,4 enchainment of resultant polymer are found to be dependent on the structure of ligand and amount of activator used. Under the optimized condition, free ortho-substitutes Cr catalysts Cr1, Cr3, Cr4 and Cr6 are capable of initiating high trans-1,4 selectivity (trans-1,4: 89.2%-92.0%) with good polymer yields (71.5%-78.0%), while counterparts with ortho-positioned alkyl groups Cr2, Cr5 and Cr7 display mixed selectivities with moderate polymer yields. The sterical effect of ligand and amount of MMAO on the catalytic performance, in particular, the stereoselectivity and polymer yield, has been also elucidated by conjugated diene polymerization mechanism. © 2014 Elsevier B.V. All rights reserved.

  5. Trans-1,4 selective polymerization of 1,3-butadiene with symmetry pincer chromium complexes activated by MMAO

    KAUST Repository

    Gong, Dirong

    2014-09-01

    Tridentate chromium complexes (Cr1-Cr7) incorporated with symmetrical pincer ligand bis(arylimino)pyridine and bis(pyrzaolyl)pyridine have been synthesized and characterized by elemental analyis, FT-IR as well as ESI-MS. X-ray diffraction reveals solids-state structures of Cr2, Cr4 and Cr6 all adopt pseudo-octahedral coordination environment with respect to metal center. All complexes have been tested in stereoregulated polymerization of butadiene under various polymerization conditions. The trans-1,4 and cis-1,4 enchainment of resultant polymer are found to be dependent on the structure of ligand and amount of activator used. Under the optimized condition, free ortho-substitutes Cr catalysts Cr1, Cr3, Cr4 and Cr6 are capable of initiating high trans-1,4 selectivity (trans-1,4: 89.2%-92.0%) with good polymer yields (71.5%-78.0%), while counterparts with ortho-positioned alkyl groups Cr2, Cr5 and Cr7 display mixed selectivities with moderate polymer yields. The sterical effect of ligand and amount of MMAO on the catalytic performance, in particular, the stereoselectivity and polymer yield, has been also elucidated by conjugated diene polymerization mechanism. © 2014 Elsevier B.V. All rights reserved.

  6. Studies on the complexes of some triphenylmethane dyes with chromium, molybdenum and tungsten

    Energy Technology Data Exchange (ETDEWEB)

    Malik, W U; Bembi, Ramesh; Bhargava, P P; Singh, R [Roorkee Univ. (India). Dept. of Chemistry

    1978-01-01

    Crystal violet, malachite green and fuchsine react with potassium chromate, sodium molybdate and sodium tungstate in 1N H/sub 2/SO/sub 4/ give 1:1 metal ligand complexes. However, in the case of chromate only an addition product with these cationic dyes is obtained. Infrared spectra of the isolated complexes show that the dyes are bound to the metal through the nitrogen atom.

  7. N-Heterocyclic carbenes on close-packed coinage metal surfaces: bis-carbene metal adatom bonding scheme of monolayer films on Au, Ag and Cu.

    Science.gov (United States)

    Jiang, Li; Zhang, Bodong; Médard, Guillaume; Seitsonen, Ari Paavo; Haag, Felix; Allegretti, Francesco; Reichert, Joachim; Kuster, Bernhard; Barth, Johannes V; Papageorgiou, Anthoula C

    2017-12-01

    By means of scanning tunnelling microscopy (STM), complementary density functional theory (DFT) and X-ray photoelectron spectroscopy (XPS) we investigate the binding and self-assembly of a saturated molecular layer of model N -heterocyclic carbene (NHC) on Cu(111), Ag(111) and Au(111) surfaces under ultra-high vacuum (UHV) conditions. XPS reveals that at room temperature, coverages up to a monolayer exist, with the molecules engaged in metal carbene bonds. On all three surfaces, we resolve similar arrangements, which can be interpreted only in terms of mononuclear M(NHC) 2 (M = Cu, Ag, Au) complexes, reminiscent of the paired bonding of thiols to surface gold adatoms. Theoretical investigations for the case of Au unravel the charge distribution of a Au(111) surface covered by Au(NHC) 2 and reveal that this is the energetically preferential adsorption configuration.

  8. Fischer aminocarbene complexes of chromium and iron: Anomalous electrochemical reduction of p-carbonyl substituted derivatives

    Czech Academy of Sciences Publication Activity Database

    Hoskovcová, I.; Zvěřinová, R.; Roháčová, J.; Dvořák, D.; Tobrman, T.; Záliš, Stanislav; Ludvík, Jiří

    2011-01-01

    Roč. 56, č. 19 (2011), s. 6853-6859 ISSN 0013-4686 R&D Projects: GA AV ČR IAA400400813 Institutional research plan: CEZ:AV0Z40400503 Keywords : DFT calculations * electrochemistry * Fischer aminocarbene complexes Subject RIV: CG - Electrochemistry Impact factor: 3.832, year: 2011

  9. Structural flexibility of 2-hetaryl chromium aminocarbene complexes: Experimental and theoretical evidence

    Czech Academy of Sciences Publication Activity Database

    Kvapilová, Hana; Eigner, V.; Hoskovcová, I.; Tobrman, T.; Čejka, J.; Záliš, Stanislav

    2014-01-01

    Roč. 421, SEP 2014 (2014), s. 439-445 ISSN 0020-1693 R&D Projects: GA MŠk LD14129 Institutional support: RVO:61388955 Keywords : Transition metal complex * Density functional theory * Potential energy surface Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.046, year: 2014

  10. Synthesis, characterization and electrochemical investigation of hetaryl chromium(0) aminocarbene complexes

    Czech Academy of Sciences Publication Activity Database

    Metelková, R.; Tobrman, T.; Kvapilová, Hana; Hoskovcová, I.; Ludvík, Jiří

    2012-01-01

    Roč. 82, SI (2012), s. 470-477 ISSN 0013-4686 R&D Projects: GA AV ČR IAA400400813 Institutional support: RVO:61388955 Keywords : Fischer aminocarbene complexes * synthesis * Electrochemical oxidation and reduction Subject RIV: CG - Electrochemistry Impact factor: 3.777, year: 2012

  11. Elucidating Bioreductive Transformations within Physically Complex Media: Impact on the Fate and Transport of Uranium and Chromium

    International Nuclear Information System (INIS)

    P.M. Jardine; T.L. Bank; M. E. Baldwin; S.E. Fendorf; M.A. Ginder-Vogel; Kukkadapu, M.E.

    2006-01-01

    The greatest challenge to elucidating geochemical and biological chromium reduction in natural sediments is to create a sterile environment without destroying the chemical and physical properties of the system. In this study we determined the potential for geochemical and biological chromium reduction in a naturally reducing soil using carbon amendments and sterilization. To minimize alterations to the sediment samples, soils were sterilized via exposure to ?-irradiation which causes fewer changes in the physical and chemical properties of the soil compared to other methods of sterilization. The objective of our research was to determine if the absence of viable microorganisms significantly affected the extent of chromium reduction in a reducing soil. Our hypothesis was that if geochemical reduction pathways dominated the system then soil sterilization should have little to no effect on the amount and rate of chromium that was reduced. However, if the reduction of chromium in these soils was a synergistic process then significantly different amounts of chromium should be reduced in the sterilized versus non-sterilized samples

  12. Unusual solvation through both p-orbital lobes of a carbene carbon

    Energy Technology Data Exchange (ETDEWEB)

    Hadad, C. Z., E-mail: cacier.hadad@udea.edu.co [Grupo de Química-Física Teórica, Instituto de Química, Universidad de Antioquia, A. A. 1226 Medellín (Colombia); Jenkins, Samantha [College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, Hunan 410081 (China); Flórez, Elizabeth [Departamento de Ciencias Básicas, Universidad de Medellín, Carrera 87 N° 30-65, Medellín (Colombia)

    2015-03-07

    As a result of a configurational space search done to explain the experimental evidence of transient specific solvation of singlet fluorocarbene amide with tetrahydrofuran, we found that the most stable structures consist in a group in which each oxygen of two tetrahydrofuran molecules act as electron donor to its respective empty p-orbital lobe of the carbene carbon atom, located at each side of the carbene molecular plane. This kind of species, which to our knowledge has not been reported before, explains very well the particular experimental characteristics observed for the transient solvation of this system. We postulate that the simultaneous interaction to both p-orbital lobes seems to confer a special stability to the solvation complexes, because this situation moves away the systems from the proximity of the corresponding transition states for the ylide products. Additionally, we present an analysis of other solvation complexes and a study of the nature of the involved interactions.

  13. Mechanistic studies on reactivities of organometallic macrocyclic complexes of chromium and cobalt

    International Nuclear Information System (INIS)

    Shi, Shu.

    1990-01-01

    Reaction pathways leading to the formation and cleavage of a transition metal-carbon bond at various oxidation states of the metal occupy a central position in understanding many enzymatic reactions and designing catalysts. The report is divided into six parts that (1) focus on the homolysis vs heterolysis of a C-Cr(III) bond, (2) describes a unique chain reaction and a S E 2 reaction I 2 and RCrL 2+ , (3) concerns the oxidation of organochromium(III) complexes by dihalide and pseudo-dihalide radical anions generated by pulse radiolysis, (4) concentrates on the oxidation mechanism of RCr(H 2 O) 2+ and the fate of RCr(H 2 O) 3+ as well as the corresponding reduction potentials, (5) extends study of organocobalt complexes with attention to reduction induced cleavages of a transition metal-carbon bond, and (6) describes the crystallization of [(CH 3 ) 4 N][Co(dmgBF 2 ) 2 py] and reports its molecular structure as determined by x-ray diffraction. 182 refs., 25 figs., 16 tabs. (BM)

  14. Mechanistic studies on reactivities of organometallic macrocyclic complexes of chromium and cobalt

    Energy Technology Data Exchange (ETDEWEB)

    Shi, Shu.

    1990-12-10

    Reaction pathways leading to the formation and cleavage of a transition metal-carbon bond at various oxidation states of the metal occupy a central position in understanding many enzymatic reactions and designing catalysts. The report is divided into six parts that (1) focus on the homolysis vs heterolysis of a C-Cr(III) bond, (2) describes a unique chain reaction and a S{sub E}2 reaction I{sub 2} and RCrL{sup 2+}, (3) concerns the oxidation of organochromium(III) complexes by dihalide and pseudo-dihalide radical anions generated by pulse radiolysis, (4) concentrates on the oxidation mechanism of RCr(H{sub 2}O){sup 2+} and the fate of RCr(H{sub 2}O){sup 3+} as well as the corresponding reduction potentials, (5) extends study of organocobalt complexes with attention to reduction induced cleavages of a transition metal-carbon bond, and (6) describes the crystallization of ((CH{sub 3}){sub 4}N)(Co(dmgBF{sub 2}){sub 2}py) and reports its molecular structure as determined by x-ray diffraction. 182 refs., 25 figs., 16 tabs. (BM)

  15. Chromium in potatoes

    International Nuclear Information System (INIS)

    Stoddard-Gilbert, K.; Blincoe, C.

    1989-01-01

    Chromium concentration in potatoes was determined, and tubes were labeled either intrinsically or extrinsically with radioactive chromate ( 51 Cr). A labeled chromium complex was isolated from preparations of raw, baked, or fried potatoes and chromatographed on gel permeation media. Potato pulp and peel contained 1.63 and 2.70 μg of Cr/g tissue, respectively. There was no correlation between the two, nor did they respond similarly to changes of variety or locations. No significant differences were apparent in relative migration of the isolated complexes except between raw and cooked extrinsically labeled preparations

  16. Magnesium analysis. Spectrophotometric determination of chromium

    International Nuclear Information System (INIS)

    Anon.

    Chromium determination in magnesium used in uranium fabrication by magnesiothermics, applicable for chromium content between 2 to 10 ppm. Magnesium is dissolved in sulfuric acid, oxidized by potassium permanganate, the excess of permanganate is eliminated by sodium nitride. Spectrophotometry at 540 nm of the chromium (VI)-diphenylcarbazide complex [fr

  17. Experimental evidence for cobalt(III)-carbene radicals: key intermediates in cobalt(II)-based metalloradical cyclopropanation

    NARCIS (Netherlands)

    Lu, H.; Dzik, W.I.; Xu, X.; Wojtas, L.; de Bruin, B.; Zhang, X.P.

    2011-01-01

    New and conclusive evidence has been obtained for the existence of cobalt(III)-carbene radicals that have been previously proposed as the key intermediates in the underlying mechanism of metalloradical cyclopropanation by cobalt(II) complexes of porphyrins. In the absence of olefin substrates,

  18. Influence of ligand-bridged substitution on the exchange coupling constant of chromium-wheels host complexes: a density functional theory study

    Science.gov (United States)

    Sadeghi Googheri, Motahare; Abolhassani, Mohammad Reza; Mirzaei, Mahmoud

    2018-05-01

    Designing and introducing novel wheel-shaped supramolecular as host complexes with new magnetic properties is the theme of the day. So in this study, new eight binuclear chromium (III) complexes, as models of real chromium-wheel host complexes, were designed based on changing of bridged-ligands and exchange coupling constants (J) of them were calculated using the broken symmetry density functional theory approach. Substitution of fluorine ligand in fluoro-bridged model [Cr2F(tBuCO2)2(H2O)2(OH)4]-1 by halogen anions (Cl-, Br- and I- ) decreased the antiferromagnetic exchange coupling between Cr(III) centres such that by going from F- to I- the J values became more positive. In the case of hydroxo-bridged model [Cr2OH(tBuCO2)2(H2O)2(OH)4]-1, replacement of hydroxyl by methoxy anion (OMe-) strengthened the antiferromagnetic property of the complex but substitution by sulfanide (SH-) and amide (NH2-) anions weakened it and changed the nature of complexes to ferromagnetic. Because of their different magnetic properties, these new investigated complexes can be suggested as interesting synthetic targets. Also, the J value changes due to ligand substitution were evaluated and it was found that the Cr-X bond strength and partial charges of involved atoms were the most effective factors on it.

  19. Functional (co)polymers from carbenes: scope, mechanism & polymer properties

    NARCIS (Netherlands)

    Franssen, N.M.G.

    2012-01-01

    Polymerization of carbenes is a valuable alternative to traditional olefin polymerization with regard to the formation of high molecular-weight functional copolymers in a stereoregular way. The versatility of this reaction with respect to different carbene precursors allows the formation of a large

  20. Interfacial charge separation and photovoltaic efficiency in Fe(ii)-carbene sensitized solar cells.

    Science.gov (United States)

    Pastore, Mariachiara; Duchanois, Thibaut; Liu, Li; Monari, Antonio; Assfeld, Xavier; Haacke, Stefan; Gros, Philippe C

    2016-10-12

    The first combined theoretical and photovoltaic characterization of both homoleptic and heteroleptic Fe(ii)-carbene sensitized photoanodes in working dye sensitized solar cells (DSSCs) has been performed. Three new heteroleptic Fe(ii)-NHC dye sensitizers have been synthesized, characterized and tested. Despite an improved interfacial charge separation in comparison to the homoleptic compounds, the heteroleptic complexes did not show boosted photovoltaic performances. The ab initio quantitative analysis of the interfacial electron and hole transfers and the measured photovoltaic data clearly evidenced fast recombination reactions for heteroleptics, even associated with un unfavorable directional electron flow, and hence slower injection rates, in the case of homoleptics. Notably, quantum mechanics calculations revealed that deprotonation of the not anchored carboxylic function in the homoleptic complex can effectively accelerate the electron injection rate and completely suppress the electron recombination to the oxidized dye. This result suggests that introduction of strong electron-donating substituents on the not-anchored carbene ligand in heteroleptic complexes, in such a way of mimicking the electronic effects of the carboxylate functionality, should yield markedly improved interfacial charge generation properties. The present results, providing for the first time a detailed understanding of the interfacial electron transfers and photovoltaic characterization in Fe(ii)-carbene sensitized solar cells, open the way to a rational molecular engineering of efficient iron-based dyes for photoelectrochemical applications.

  1. A non-diazo approach to α-oxo gold carbenes via gold-catalyzed alkyne oxidation.

    Science.gov (United States)

    Zhang, Liming

    2014-03-18

    For the past dozen years, homogeneous gold catalysis has evolved from a little known topic in organic synthesis to a fully blown research field of significant importance to synthetic practitioners, due to its novel reactivities and reaction modes. Cationic gold(I) complexes are powerful soft Lewis acids that can activate alkynes and allenes toward efficient attack by nucleophiles, leading to the generation of alkenyl gold intermediates. Some of the most versatile aspects of gold catalysis involve the generation of gold carbene intermediates, which occurs through the approach of an electrophile to the distal end of the alkenyl gold moiety, and their diverse transformations thereafter. On the other hand, α-oxo metal carbene/carbenoids are highly versatile intermediates in organic synthesis and can undergo various synthetically challenging yet highly valuable transformations such as C-H insertion, ylide formation, and cyclopropanation reactions. Metal-catalyzed dediazotizations of diazo carbonyl compounds are the principle and most reliable strategy to access them. Unfortunately, the substrates contain a highly energetic diazo moiety and are potentially explosive. Moreover, chemists need to use energetic reagents to prepare them, putting further constrains on operational safety. In this Account, we show that the unique access to the gold carbene species in homogeneous gold catalysis offers an opportunity to generate α-oxo gold carbenes if both nucleophile and electrophile are oxygen. Hence, this approach would enable readily available and safer alkynes to replace hazardous α-diazo carbonyl compounds as precursors in the realm of gold carbene chemistry. For the past several years, we have demonstrated that alkynes can indeed effectively serve as precursors to versatile α-oxo gold carbenes. In our initial study, we showed that a tethered sulfoxide can be a suitable oxidant, which in some cases leads to the formation of α-oxo gold carbene intermediates. The

  2. A Non-Diazo Approach to α-Oxo Gold Carbenes via Gold-Catalyzed Alkyne Oxidation

    Science.gov (United States)

    2015-01-01

    For the past dozen years, homogeneous gold catalysis has evolved from a little known topic in organic synthesis to a fully blown research field of significant importance to synthetic practitioners, due to its novel reactivities and reaction modes. Cationic gold(I) complexes are powerful soft Lewis acids that can activate alkynes and allenes toward efficient attack by nucleophiles, leading to the generation of alkenyl gold intermediates. Some of the most versatile aspects of gold catalysis involve the generation of gold carbene intermediates, which occurs through the approach of an electrophile to the distal end of the alkenyl gold moiety, and their diverse transformations thereafter. On the other hand, α-oxo metal carbene/carbenoids are highly versatile intermediates in organic synthesis and can undergo various synthetically challenging yet highly valuable transformations such as C–H insertion, ylide formation, and cyclopropanation reactions. Metal-catalyzed dediazotizations of diazo carbonyl compounds are the principle and most reliable strategy to access them. Unfortunately, the substrates contain a highly energetic diazo moiety and are potentially explosive. Moreover, chemists need to use energetic reagents to prepare them, putting further constrains on operational safety. In this Account, we show that the unique access to the gold carbene species in homogeneous gold catalysis offers an opportunity to generate α-oxo gold carbenes if both nucleophile and electrophile are oxygen. Hence, this approach would enable readily available and safer alkynes to replace hazardous α-diazo carbonyl compounds as precursors in the realm of gold carbene chemistry. For the past several years, we have demonstrated that alkynes can indeed effectively serve as precursors to versatile α-oxo gold carbenes. In our initial study, we showed that a tethered sulfoxide can be a suitable oxidant, which in some cases leads to the formation of α-oxo gold carbene intermediates. The

  3. Anti-diabetic effects of Inonotus obliquus polysaccharides-chromium (III) complex in type 2 diabetic mice and its sub-acute toxicity evaluation in normal mice.

    Science.gov (United States)

    Wang, Cong; Chen, Zhongqin; Pan, Yuxiang; Gao, Xudong; Chen, Haixia

    2017-10-01

    Polysaccharides are important bioactive ingredients from Inonotus obliquus. This study aimed to synthesize and characterize a novel I. obliquus polysaccharides-chromium (III) complex (UIOPC) and investigate the anti-diabetic effects in streptozotocin (STZ) induced type 2 diabetes mellitus (T2DM) mice and sub-acute toxicity in normal mice. The molecular weight of UIOPC was about 11.5 × 10 4  Da with the chromium content was 13.01% and the chromium was linked with polysaccharides through coordination bond. After treatment of UIOPC for four weeks, the body weight, fasting blood glucose (FBG) levels, plasma insulin levels of the diabetic mice were significantly reduced when compared with those of the diabetic mice (p < 0.05). The results on serum profiles and antioxidant enzymes activities revealed that UIOPC had a positive effect on hypoglycemic and antioxidant ability. Histopathology results showed that UIOPC could effectively alleviate the STZ-lesioned tissues in diabetic mice. Furthermore, high dose administration of UIOPC had no obviously influence on serum profiles levels and antioxidant ability of the normal mice and the organ tissues maintained organized and integrity in the sub-acute toxicity study. These results suggested that UIOPC might be a good candidate for the functional food or pharmaceuticals in the treatment of T2DM. Copyright © 2017 Elsevier Ltd. All rights reserved.

  4. Chromium allergy

    DEFF Research Database (Denmark)

    Hansen, M B; Johansen, J D; Menné, Torkil

    2003-01-01

    Most studies investigating chromium allergy have been performed with Cr(VI). However, real exposure to chromium from leather products includes both Cr(III) and Cr(VI). We have determined and compared the minimum elicitation threshold (MET) concentration for Cr(III) and Cr(VI) in Cr(VI)-sensitive ......Most studies investigating chromium allergy have been performed with Cr(VI). However, real exposure to chromium from leather products includes both Cr(III) and Cr(VI). We have determined and compared the minimum elicitation threshold (MET) concentration for Cr(III) and Cr(VI) in Cr......(III) was concluded to play an important role in chromium allergy, because Cr(III) and Cr(VI) were both capable of eliciting eczema at low concentrations. Rather than regarding chromium dermatitis as a result of Cr(VI) allergy alone, it may be more correct to consider it as a result of a combined Cr(III) and Cr......(VI) allergy....

  5. An investigation of the chromium oxidation state of a monoanionic chromium tris(catecholate) complex by X-ray absorption and EPR spectroscopies

    DEFF Research Database (Denmark)

    Pattison, D I; Levina, A; Davies, Michael Jonathan

    2001-01-01

    The well-known monoanionic Cr tris(3,5-di-tert-butylcatecholato) complex, [Cr(DTBC)3]-, has been studied by X-ray absorption spectroscopy. The multiple-scattering fit to the XAFS gave good correlation (R = 19.8%) and good values for all of the bond lengths, angles, and Debye-Waller factors. The p...

  6. Bimolecular reactions of carbenes: Proton transfer mechanism

    Science.gov (United States)

    Abu-Saleh, Abd Al-Aziz A.; Almatarneh, Mansour H.; Poirier, Raymond A.

    2018-04-01

    Here we report the bimolecular reaction of trifluoromethylhydroxycarbene conformers and the water-mediated mechanism of the 1,2-proton shift for the unimolecular trans-conformer by using quantum chemical calculations. The CCSD(T)/cc-pVTZ//MP2/cc-pVDZ potential-energy profile of the bimolecular reaction of cis- and trans-trifluoromethylhydroxycarbene, shows the lowest gas-phase barrier height of 13 kJ mol-1 compared to the recently reported value of 128 kJ mol-1 for the unimolecular reaction. We expect bimolecular reactions of carbene's stereoisomers will open a valuable field for new and useful synthetic strategies.

  7. Study of color parameters of light exposed and light exposed wool fabrics dyed with 1:1 chromium (III) based complex dyes

    International Nuclear Information System (INIS)

    Kausar, N.; Ahmad, M.A.; Wahab, M.A.

    2009-01-01

    Derivatives of a-amino benzoic acid (anthranilic acid) were synthesized using 1-naphthol-3,6-disulfonic acid, 1-Naphthol-8 amino-3, 6-di-sulfonic acid; 1-naphthol-3-sulfonic acid, 6-methylamino-1-naphthol-3-sulfonic acid or 1-naphthol-3-sulfonic acid, 6-phenylamino-l-naphthol-3-sulfonic acid as a coupling component. These derivatives were used to synthesize chromium (Ill) complexes. After isolation, these complexes were applied on pure wool fabric by exhaust process to evaluate hue, wash fastness and light fastness properties. The complexes delivered a change in color equivalent to gray scale step 3/5 to 4/5 for wash fastness test. During the study of light fastness, it was monitored that the hue of dyed fabrics enhanced after exposing them to Light. (author)

  8. Reaction of CO2 with propylene oxide and styrene oxide catalyzed by a chromium(III) amine-bis(phenolate) complex.

    Science.gov (United States)

    Dean, Rebecca K; Devaine-Pressing, Katalin; Dawe, Louise N; Kozak, Christopher M

    2013-07-07

    A diamine-bis(phenolate) chromium(III) complex, {CrCl[O2NN'](BuBu)}2 catalyzes the copolymerization of propylene oxide with carbon dioxide. The synthesis of this metal complex is straightforward and it can be obtained in high yields. This catalyst incorporates a tripodal amine-bis(phenolate) ligand, which differs from the salen or salan ligands typically used with Cr and Co complexes that have been employed as catalysts for the synthesis of such polycarbonates. The catalyst reported herein yields low molecular weight polymers with narrow polydispersities when the reaction is performed at room temperature. Performing the reaction at elevated temperatures causes the selective synthesis of propylene carbonate. The copolymerization activity for propylene oxide and carbon dioxide, as well as the coupling of carbon dioxide and styrene oxide to give styrene carbonate are presented.

  9. Carbene Transfer Reactions Catalysed by Dyes of the Metalloporphyrin Group

    Directory of Open Access Journals (Sweden)

    Mário M. Q. Simões

    2018-03-01

    Full Text Available Carbene transfer reactions are very important transformations in organic synthesis, allowing the generation of structurally challenging products by catalysed cyclopropanation, cyclopropenation, carbene C-H, N-H, O-H, S-H, and Si-H insertion, and olefination of carbonyl compounds. In particular, chiral and achiral metalloporphyrins have been successfully explored as biomimetic catalysts for these carbene transfer reactions under both homogeneous and heterogeneous conditions. In this work the use of synthetic metalloporphyrins (MPorph, M = Fe, Ru, Os, Co, Rh, Ir, Sn as homogeneous or heterogeneous catalysts for carbene transfer reactions in the last years is reviewed, almost exclusively focused on the literature since the year 2010, except when reference to older publications was deemed to be crucial.

  10. Atom states and interatomic interactions in complex perovskite-like oxides. Communication XX. Origin of electron-ionic conductivity in lanthanum gallates doped with strontium and chromium

    International Nuclear Information System (INIS)

    Chezhina, N.V.; Zolotukhina, N.V.; Pijr, I.V.

    2006-01-01

    Magnetic susceptibilities and electric conductivities of solid solutions based on lanthanum gallate containing chromium and strontium atoms in the ratio of 10 : 2 were studied. It was shown that no partial oxidation of chromium to Cr(IV) occurs when lanthanum gallate is doped with chromium and strontium simultaneously, whereas the ionic conductivity is associated with the appearance of vacancies stabilized by chromium atoms in the oxygen sublattice [ru

  11. Latent ruthenium–indenylidene catalysts bearing a N-heterocyclic carbene and a bidentate picolinate ligand

    Directory of Open Access Journals (Sweden)

    Thibault E. Schmid

    2015-09-01

    Full Text Available A silver-free methodology was developed for the synthesis of unprecedented N-heterocyclic carbene ruthenium indenylidene complexes bearing a bidentate picolinate ligand. The highly stable (SIPr(picolinateRuCl(indenylidene complex 4a (SIPr = 1,3-bis(2-6-diisopropylphenylimidazolidin-2-ylidene demonstrated excellent latent behaviour in ring closing metathesis (RCM reaction and could be activated in the presence of a Brønsted acid. The versatility of the catalyst 4a was subsequently demonstrated in RCM, cross-metathesis (CM and enyne metathesis reactions.

  12. Arylation of Rhodium(II) Azavinyl Carbenes with Boronic Acids

    Science.gov (United States)

    Selander, Nicklas; Worrell, Brady T.; Chuprakov, Stepan; Velaparthi, Subash; Fokin, Valery V.

    2013-01-01

    A highly efficient and stereoselective arylation of in situ generated azavinyl carbenes affording 2,2-diaryl enamines at ambient temperatures has been developed. These transition metal carbenes are directly produced from readily available and stable 1-sulfonyl-1,2,3-triazoles in the presence of a rhodium carboxylate catalyst. In several cases, the enamines generated in this reaction can be cyclized into substituted indoles employing copper catalysts. PMID:22913576

  13. The effects of chromium complex and level on glucose metabolism and memory acquisition in rats fed high-fat diet.

    Science.gov (United States)

    Sahin, Kazim; Tuzcu, Mehmet; Orhan, Cemal; Agca, Can A; Sahin, Nurhan; Guvenc, Mehmet; Krejpcio, Zbigniew; Staniek, Halina; Hayirli, Armagan

    2011-11-01

    Conditions in which glucose metabolism is impaired due to insulin resistance are associated with memory impairment. It was hypothesized that supplemental chromium (Cr) may alleviate insulin resistance in type 2 diabetes and consequently improve memory acquisition, depending upon its source and level. In a complete randomized design experiment, male Wistar rats (n=60; weighing 200-220 g) were fed either normal (8%, normal diet (ND)) or high-fat (40%, high-fat diet (HFD)) diet and supplemented with Cr as either chromium-glycinate (CrGly) or chromium-acetate (CrAc) at doses of 0, 40, or 80 μg/kg body weight (BW) via drinking water from 8 to 20 weeks of age. Feeding HFD induced type 2 diabetes, as reflected by greater glucose/insulin ratio (2.98 vs. 2.74) comparing to feeding ND. Moreover, HFD rats had greater BW (314 vs. 279 g) and less serum (53 vs. 68 μg/L) and brain (14 vs. 24 ng/g) Cr concentrations than ND rats. High-fat diet caused a 32% reduction in expressions of glucose transporters 1 and 3 (GLUTs) in brain tissue and a 27% reduction in mean percentage time spent in the target quadrant and a 38% increase in spatial memory acquisition phase (SMAP) compared with ND. Compared with supplemental Cr as CrAc, CrGly was more effective to ameliorate response variables (i.e., restoration of tissue Cr concentration, enhancement of cerebral GLUTs expressions, and reduction of the glucose/insulin ratio and SMAP) in a dose-response manner, especially in rats fed HFD. Supplemental Cr as CrGly may have therapeutic potential to enhance insulin action and alleviate memory acquisition in a dose-dependent manner, through restoring tissue Cr reserve and enhancing cerebral GLUTs expressions.

  14. N,N'-diamidoketenimines via coupling of isocyanides to an N-heterocyclic carbene.

    Science.gov (United States)

    Hudnall, Todd W; Moorhead, Eric J; Gusev, Dmitry G; Bielawski, Christopher W

    2010-04-16

    Treatment of an N-heterocyclic carbene that features two amide groups N-bound to the carbene nucleus with various organic isocyanides afforded a new class of ketenimines in yields of up to 96% (isolated). DFT analyses revealed that the carbene exhibits a unique, low-lying LUMO, which may explain the atypical reactivity observed.

  15. Manganese Fischer carbene chemistry: Reactions of Cp prime (CO) sub 2 Mn double bond C(OMe/OLi)R with enynes, 1-hexyne, and acrylates

    Energy Technology Data Exchange (ETDEWEB)

    Hoye, T.R.; Rehberg, G.M. (Univ. of Minnesota, Minneapolis (United States))

    1990-12-01

    Reactions of manganese carbene complexes, both the neutral methoxy and anionic lithoxy' versions, with {alpha},{omega}-enzymes give bicyclic cyclopropanes. The anion also reacts with 1-hexyne to give butenolide and with acrylate esters to give {gamma}-keto esters.

  16. Synthesis of axially chiral oxazoline-carbene ligands with an N-naphthyl framework and a study of their coordination with AuCl·SMe(2).

    Science.gov (United States)

    Wang, Feijun; Li, Shengke; Qu, Mingliang; Zhao, Mei-Xin; Liu, Lian-Jun; Shi, Min

    2012-01-01

    Axially chiral oxazoline-carbene ligands with an N-naphthyl framework were successfully prepared, and their coordination behavior with AuCl·SMe(2) was also investigated, affording the corresponding Au(I) complexes in moderate to high yields.

  17. Evaluation of an olefin metathesis pre-catalyst with a bulky and electron-rich N-heterocyclic carbene

    KAUST Repository

    Manzini, Simone

    2015-03-01

    The commercially-available metathesis pre-catalyst M23 has been evaluated alongside new complex [RuCl2((3-phenyl)indenylidene)(PPh3)(SIPrOMe)] (1), which bears a para-methoxy-substituted N-heterocyclic carbene ligand. Several model metathesis reactions could be conducted using only parts-per-million levels of ruthenium catalyst. The effects of the different NHC ligands on reactivity have been explored.

  18. Evaluation of an olefin metathesis pre-catalyst with a bulky and electron-rich N-heterocyclic carbene

    KAUST Repository

    Manzini, Simone; Urbina Blanco, Cé sar A.; Nelson, David J.; Poater, Albert; Lebl, Tomas; Meiries, Sé bastien; Slawin, Alexandra M.Z.; Falivene, Laura; Cavallo, Luigi; Nolan, Steven P.

    2015-01-01

    The commercially-available metathesis pre-catalyst M23 has been evaluated alongside new complex [RuCl2((3-phenyl)indenylidene)(PPh3)(SIPrOMe)] (1), which bears a para-methoxy-substituted N-heterocyclic carbene ligand. Several model metathesis reactions could be conducted using only parts-per-million levels of ruthenium catalyst. The effects of the different NHC ligands on reactivity have been explored.

  19. Cascade olefin isomerization/intramolecular Diels-Alder reaction catalyzed by N-heterocyclic carbenes.

    Science.gov (United States)

    Kowalczyk, Marcin; Lupton, David W

    2014-05-19

    The addition of an N-heterocyclic carbene to the carbonyl group of an α,β,γ,δ-unsaturated enol ester affords a hemiacetal azolium intermediate that enables a cascade olefin isomerization/Diels-Alder reaction, for which mechanistic studies implicate Lewis base catalysis. Preliminary studies into the utility of the products have been undertaken with reductive and oxidative cleavage, giving materials for potential use in complex-target synthesis. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. A DFT Study on Selected Physical Organic Aspects of the Fischer Carbene Intermediates [(M(CO4(C(OMeMe

    Directory of Open Access Journals (Sweden)

    Tareq Irshaidat

    2010-01-01

    Full Text Available Fischer carbenes are important starting materials for C-C bond formation via coupling reactions between carbene and wide variety of substituted alkenes or alkynes. This DFT study shed light on unique fundamental organic/organometallic aspects for the C(OMeMe carbene in the free form and in case of bonding with M(CO4 (M= Cr, Mo, W. The data illustrate that the structures of the title intermediates include a unique structure stabilizing intramolecular M…C-H interaction (agostic interaction. This conclusion was made based on calculated NMR data (for carbon and hydrogen, structural parameters, energy calculations of conformers (C-C conformation, selected IR stretching frequencies (C-O, C-C, and C-H, and atomic charges. The agostic interaction is most efficient in case of chromium and in general is described as an overlap between the σ-bond electron pair of C-H with an empty d-orbital of the metal. These characterized examples are new addition to the orbital interaction theory.

  1. A theobromine derived silver N-heterocyclic carbene: synthesis, characterization, and antimicrobial efficacy studies on cystic fibrosis relevant pathogens†

    Science.gov (United States)

    Panzner, Matthew J.; Hindi, Khadijah M.; Wright, Brian D.; Taylor, Jane B.; Han, Daniel S.

    2009-01-01

    The increasing incidence of multidrug-resistant (MDR) pulmonary infections in the cystic fibrosis (CF) population has prompted the investigation of innovative silver based therapeutics. The functionalization of the naturally occurring xanthine theobromine at the N1 nitrogen atom with an ethanol substituent followed by the methylation of the N9 nitrogen atom gives the N-heterocyclic carbene precursor 1-(2-hydroxyethyl)-3,7,9-trimethylxanthinium iodide. The reaction of this xanthinium salt with silver acetate produces the highly hydrophilic silver carbene complex SCC8. The in vitro antimicrobial efficacy of this newly synthesized complex was evaluated with excellent results on a variety of virulent and MDR pathogens isolated from CF patients. A comparative in vivo study between the known caffeine derived silver carbene SCC1 and SCC8 demonstrated the ability of both complexes to improve the survival rates of mice in a pneumonia model utilizing the clinically isolated infectious strain of Pseudomonas aeruginosa PA M57-15. PMID:20449175

  2. The influence of a selenium-chromium-lipid complex obtained from Chlorella vulgaris on the energy metabolism in rats with experimental diabetes

    Directory of Open Access Journals (Sweden)

    O. Y. Lukashiv

    2017-07-01

    Full Text Available One of the leading roles in treating diabetes mellitus belongs to chrome ions therapy (III, especially in the complex with selenium (IV. Currently selenium is obtained from unicellular algae, which contain biologically active substances and which are capable of accumulating exogenous microelements. By incubating unicellular algae Chlorella vulgaris Biej. in the conditions of aquaculture with sodium selenite (IV and chromium (III chloride, we obtained a biologically active lipid substance which contains selenium and chromium. The substance was tested for the impact on energy metabolism of animals exposed to experimentally induced diabetes mellitus. The diabetes was caused by modeling obesity of the animals with further injection of streptozotocin in the amount of 65 mg/kg and nicotinamide at the dose of 230 mg/kg. The rats were intragastrically injected with 1 ml of 1% starch solution which contained a selenium-chrome-lipid complex extracted from the Chlorella containing 0.6 µg of selenium, 1.05 µg of chrome and 0.5 mg of lipids for prophylactic, therapeutic and prophylactic-therapeutic purposes; the other group of rats for therapeutic purposes was injected with starch solution with the same composition of microelements in inorganic form – sodium selenite (IV and chromium chloride (III. This paper presents the results of our study of the impact of organic and inorganic compounds of chrome and selenium on the energetic metabolism of rats exposed to experimental diabetes mellitus. The analysis determined that in the rats’ organism, the selenium-chrome-lipid complex from the Chlorella improved the indicators of the energetic metabolism – in the group of rats which received it for therapeutic purposes, we observed an up to 7.5 fold increase in the activity of succinate dehydrogenase compared to the rats which did not receive therapeutic treatment. The increase in the activity of succinate dehydrogenase corresponded to the increase in the

  3. Chromium(0), molybdenum(0), and tungsten(0) isocyanide complexes as luminophores and photosensitizers with long-lived excited states

    International Nuclear Information System (INIS)

    Bueldt, Laura A.; Wenger, Oliver S.

    2017-01-01

    Arylisocyanide complexes based on earth-abundant Group 6 d 6 metals are interesting alternatives to photoactive complexes made from precious metals such as Ru II , Re I , Os II , or Ir III . Some of these complexes have long-lived 3 MLCT excited states that exhibit luminescence with good quantum yields as well as nano- to microsecond lifetimes, and they are very strongly reducing. Recent studies have demonstrated that Cr 0 , Mo 0 , and W 0 arylisocyanide complexes have great potential for applications in luminescent devices, photoredox catalysis, and dye-sensitized solar cells. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  4. In Silico Olefin Metathesis with Ru-Based Catalysts Containing N-Heterocyclic Carbenes Bearing C60Fullerenes

    KAUST Repository

    Martínez, Juan Pablo

    2016-04-10

    Density functional theory calculations have been used to explore the potential of Ru-based complexes with 1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene (SIMes) ligand backbone (A) being modified in silico by the insertion of a C60 molecule (B and C), as olefin metathesis catalysts. To this end, we investigated the olefin metathesis reaction catalyzed by complexes A, B, and C using ethylene as the substrate, focusing mainly on the thermodynamic stability of all possible reaction intermediates. Our results suggest that complex B bearing an electron-withdrawing N-heterocyclic carbene improves the performance of unannulated complex A. The efficiency of complex B is only surpassed by complex A when the backbone of the N-heterocyclic carbene of complex A is substituted by two amino groups. The particular performance of complexes B and C has to be attributed to electronic factors, that is, the electronic-donating capacity of modified SIMes ligand rather than steric effects, because the latter are predicted to be almost identical for complexes B and C when compared to those of A. Overall, this study indicates that such Ru-based complexes B and C might have the potential to be effective olefin metathesis catalysts. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. In Silico Olefin Metathesis with Ru-Based Catalysts Containing N-Heterocyclic Carbenes Bearing C60Fullerenes

    KAUST Repository

    Martí nez, Juan Pablo; Vummaleti, Sai V. C.; Falivene, Laura; Nolan, Steven P.; Cavallo, Luigi; Solà , Miquel; Poater, Albert

    2016-01-01

    Density functional theory calculations have been used to explore the potential of Ru-based complexes with 1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene (SIMes) ligand backbone (A) being modified in silico by the insertion of a C60 molecule (B and C), as olefin metathesis catalysts. To this end, we investigated the olefin metathesis reaction catalyzed by complexes A, B, and C using ethylene as the substrate, focusing mainly on the thermodynamic stability of all possible reaction intermediates. Our results suggest that complex B bearing an electron-withdrawing N-heterocyclic carbene improves the performance of unannulated complex A. The efficiency of complex B is only surpassed by complex A when the backbone of the N-heterocyclic carbene of complex A is substituted by two amino groups. The particular performance of complexes B and C has to be attributed to electronic factors, that is, the electronic-donating capacity of modified SIMes ligand rather than steric effects, because the latter are predicted to be almost identical for complexes B and C when compared to those of A. Overall, this study indicates that such Ru-based complexes B and C might have the potential to be effective olefin metathesis catalysts. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Determination of stability constants of iron(III and chromium(III-nitrilotriacetate-methyl cysteine mixed complexes by electrophoretic technique

    Directory of Open Access Journals (Sweden)

    Brij Bhushan Tewari

    2004-06-01

    Full Text Available The stability constants of Fe(III and Cr(III with methyl cysteine and nitrilotriacetate (NTA were determined by paper electrophoretic technique. Beside binary ternary complexes have also been studied, in which nitrilotriacetate and methyl cysteine acts as primary and secondary ligand, respectively. The stability constants of mixed ligand complexes metal (M-nitrilotriacetate-methyl cysteine have been found to be 5.72 plus or minus 0.09 and 5.54 plus or minus 0.11 (log K values for Fe(III and Cr(III complexes, respectively, at 35 oC and ionic strength 0.1 M.

  7. Unsaturated carbone and allenylidene ruthenium complexes from alkynes

    International Nuclear Information System (INIS)

    Bozek, Yu.L.; Diznev, P.A.

    1995-01-01

    The author's studies aimed at activation of terminal alkynes by metal complexes, reactivity patterns and selective preparations of unsaturated carbene, allenylidene and cumulenylidene derivatives of (arene)ruthenium complexes are reviewed. 48 refs

  8. Chromium(0), molybdenum(0), and tungsten(0) isocyanide complexes as luminophores and photosensitizers with long-lived excited states

    Energy Technology Data Exchange (ETDEWEB)

    Bueldt, Laura A. [Institute of Inorganic Chemistry, University of Tuebingen, Auf der Morgenstelle 18, 72076, Tuebingen (Germany); Wenger, Oliver S. [Department of Chemistry, University of Basel, St. Johanns-Ring 19, 4056, Basel (Switzerland)

    2017-05-15

    Arylisocyanide complexes based on earth-abundant Group 6 d{sup 6} metals are interesting alternatives to photoactive complexes made from precious metals such as Ru{sup II}, Re{sup I}, Os{sup II}, or Ir{sup III}. Some of these complexes have long-lived {sup 3}MLCT excited states that exhibit luminescence with good quantum yields as well as nano- to microsecond lifetimes, and they are very strongly reducing. Recent studies have demonstrated that Cr{sup 0}, Mo{sup 0}, and W{sup 0} arylisocyanide complexes have great potential for applications in luminescent devices, photoredox catalysis, and dye-sensitized solar cells. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  9. Solvent mimicry with methylene carbene to probe protein topography.

    Science.gov (United States)

    Gómez, Gabriela Elena; Monti, José Luis E; Mundo, Mariana Rocío; Delfino, José María

    2015-10-06

    The solvent accessible surface area (SASA) of the polypeptide chain plays a key role in protein folding, conformational change, and interaction. This fundamental biophysical parameter is elusive in experimental measurement. Our approach to this problem relies on the reaction of the minimal photochemical reagent diazirine (DZN) with polypeptides. This reagent (i) exerts solvent mimicry because its size is comparable to water and (ii) shows scant chemical selectivity because it generates extremely reactive methylene carbene. Methylation gives rise to the EM (extent of modification) signal, which is useful for scrutinizing the conformational change triggered by Ca(2+) binding to calmodulin (CaM). The increased EM observed for the full protein is dominated by the enhanced exposure of hydrophobic area in Ca(2+)-CaM. Fragmentation allowed us to quantify the methylene incorporation at specific sites. Peptide 91-106 reveals a major reorganization around the calcium 151 binding site, resulting in local ordering and a greater exposure of the hydrophobic surface. Additionally, this technique shows a high sensitivity to probe recognition between CaM and melittin (Mel). The large decrease in EM indicates the occlusion of a significant hydrophobic area upon complexation. Protection from labeling reveals a larger involvement of the N-terminal and central regions of CaM in this interaction. Despite its smaller size, Mel's differential exposure can also be quantified. Moreover, MS/MS fragmentation realizes the goal of extending the resolution of labeled sites at the amino acid level. Overall, DZN labeling emerges as a useful footprinting method capable of shedding light on physiological conformational changes and interactions.

  10. Fundamental spectroscopic studies of carbenes and hydrocarbon radicals

    Energy Technology Data Exchange (ETDEWEB)

    Gottlieb, C.A.; Thaddeus, P. [Harvard Univ., Cambridge, MA (United States)

    1993-12-01

    Highly reactive carbenes and carbon-chain radicals are studied at millimeter wavelengths by observing their rotational spectra. The purpose is to provide definitive spectroscopic identification, accurate spectroscopic constants in the lowest vibrational states, and reliable structures of the key intermediates in reactions leading to aromatic hydrocarbons and soot particles in combustion.

  11. The reactions of anthronylidene carbene with some heterocyclic compounds

    International Nuclear Information System (INIS)

    Divisia, Bernadette

    1970-01-01

    The action of the anthronylidene carbene, generated by photochemical decomposition of 9-diazo 10-anthron, on four heterocyclic compounds (furan, thiophene, 1-methyl-pyrrole and 2,5-dihydrofuran) has been examined. Two classical carbene reactions have been observed: the addition on double bond (furan, thiophene, 1-methylpyrrole) and hydrogen atom abstraction of the heterocyclic compound (2,5-dihydrofuran). In the case of furan and thiophene, the cyclo-propanic compound resulting from the addition is spontaneously transformed into an ethylenic derivative by valence isomerization. The furan derivative undergoes a cis-trans isomerization, while the thiophene one undergoes an extra carbene attack. In the case of 1-methylpyrrole, the corresponding cyclo-propanic compound undergoes a ring cleavage, followed by a hydrogen atom migration leading to the formation of a substituted anthron. Only an allylic hydrogen atom selective abstraction of heterocyclic compound takes place in the reaction of anthronylidene carbene with 2,5-dihydrofuran. The asymmetrical coupling of radicals so obtained yields the corresponding substituted anthron. (author) [fr

  12. Fullerene–Carbene Lewis Acid–Base Adducts

    KAUST Repository

    Li, Huaping; Risko, Chad; Seo, Jung Hwa; Campbell, Casey; Wu, Guang; Brédas, Jean-Luc; Bazan, Guillermo C.

    2011-01-01

    The reaction between a bulky N-heterocylic carbene (NHC) and C60 leads to the formation of a thermally stable zwitterionic Lewis acid-base adduct that is connected via a C-C single bond. Low-energy absorption bands with weak oscillator strengths

  13. Chromium Salen Mediated Alkene Epoxidation

    DEFF Research Database (Denmark)

    Petersen, Kaare Brandt; Norrby, Per-Ola; Daly, Adrian M.

    2002-01-01

    The mechanism of alkene epoxidation by chromium(v) oxo salen complexes has been studied by DFT and experimental methods. The reaction is compared to the closely related Mn-catalyzed process in an attempt to understand the dramatic difference in selectivity between the two systems. Overall......-spin surface. The low-spin addition of metal oxo species to an alkene leads to an intermediate which forms epoxide either with a barrier on the low-spin surface or without a barrier after spin inversion. Supporting evidence for this intermediate was obtained by using vinylcyclopropane traps. The chromium...

  14. Simultaneous biosynthesis of putrebactin, avaroferrin and bisucaberin by Shewanella putrefaciens and characterisation of complexes with iron(III), molybdenum(VI) or chromium(V).

    Science.gov (United States)

    Soe, Cho Zin; Telfer, Thomas J; Levina, Aviva; Lay, Peter A; Codd, Rachel

    2016-09-01

    Cultures of Shewanella putrefaciens grown in medium containing 10mM 1,4-diamino-2-butanone (DBO) as an inhibitor of ornithine decarboxylase and 10mM 1,5-diaminopentane (cadaverine) showed the simultaneous biosynthesis of the macrocyclic dihydroxamic acids: putrebactin (pbH 2 ), avaroferrin (avH 2 ) and bisucaberin (bsH 2 ). The level of DBO did not completely repress the production of endogenous 1,4-diaminobutane (putrescine) as the native diamine substrate of pbH 2 . The relative concentration of pbH 2 :avH 2 :bsH 2 was 1:2:1, which correlated with the substrate selection of putrescine:cadaverine in a ratio of 1:1. The macrocycles were characterised using LC-MS as free ligands and as 1:1 complexes with Fe(III) of the form [Fe(pb)] + , [Fe(av)] + or [Fe(bs)] + , with labile ancillary ligands in six-coordinate complexes displaced during ESI-MS acquisition; or with Mo(VI) of the form [Mo(O) 2 (pb)], [Mo(O) 2 (av)] or [Mo(O) 2 (bs)]. Chromium(V) complexes of the form [CrO(pb)] + were detected from solutions of Cr(VI) and pbH 2 in DMF using X-band EPR spectroscopy. Supplementation of S. putrefaciens medium with DBO and 1,3-diaminopropane, 1,6-diaminohexane or 1,4-diamino-2(Z)-butene (Z-DBE) resulted only in the biosynthesis of pbH 2 . The work has identified a native system for the simultaneous biosynthesis of a suite of three macrocyclic dihydroxamic acid siderophores and highlights both the utility of precursor-directed biosynthesis for expanding the structural diversity of siderophores, and the breadth of their coordination chemistry. Copyright © 2015 Elsevier Inc. All rights reserved.

  15. Removal combined with reduction of hexavalent chromium from aqueous solution by Fe-ethylene glycol complex microspheres

    Science.gov (United States)

    Zhang, Yong-Xing; Jia, Yong

    2016-12-01

    Three-dimensional Fe-ethylene glycol (Fe-EG) complex microspheres were synthesized by a facile hydrothermal method, and were characterized by field emission scanning electron microscopy and transmission electron microscopy. The adsorption as well as reduction properties of the obtained Fe-EG complex microspheres towards Cr(VI) ions were studied. The experiment data of adsorption kinetic and isotherm were fitted by nonlinear regression approach. In neutral condition, the maximum adsorption capacity was 49.78 mg g-1 at room temperature, and was increased with the increasing of temperature. Thermodynamic parameters including the Gibbs free energy, standard enthalpy and standard entropy revealed that adsorption of Cr(VI) was a feasible, spontaneous and endothermic process. Spectroscopic analysis revealed the adsorption of Cr(VI) was a physical adsorption process. The adsorbed CrO42- ions were partly reduced to Cr(OH)3 by Fe(II) ions and the organic groups in the Fe-EG complex.

  16. THE DYNAMICS SORPTION FEATURES OF A COMPLEX 1,5- DIPHENILCARBAZONATE CHROMIUM(III BY USING ION-EXCHANGE RESINS CU-2-8 AND CB-4P-2 FROM DIFFERENT CATEGORIES OF WATER

    Directory of Open Access Journals (Sweden)

    Н. M. Guzenko

    2014-12-01

    Full Text Available The formation mechanism features of adsorption layers are established on a surface ionexchange resins CU-2-8 and CB-4p-2 in the presence of the inorganic ions amount, that are typical for natural and sewage water by using the dynamic and kinetic graphs considering change of complex 1,5-diphenylcarbazonate of chromium(III quantity, and also factor of sorption process speed.

  17. Studying the causes of high chromium concentration in the leather production process at Tehran Charmshahr industrial complex

    Directory of Open Access Journals (Sweden)

    M. Mahdiabadi

    2016-04-01

      Results: The results indicated the existence of toxic pollutants such as Cr+3 and Cr+6 in leather wastewater, the relatively high level of organic loads with low biodegradability, high levels of COD, BOD, TDS and finally the complexity of the treatment of wastewater.

  18. Removal combined with reduction of hexavalent chromium from aqueous solution by Fe-ethylene glycol complex microspheres

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yong-Xing [School of Physics and Electronic Information, Huaibei Normal University, Huaibei 235000 (China); Jia, Yong, E-mail: yjiaahedu@163.com [School of Pharmacy, Anhui University of Chinese Medicine, Hefei 230012 (China)

    2016-12-15

    Highlights: • Fe-EG complex microspheres were synthesized by a hydrothermal method. • The removal properties towards Cr(VI) ions were investigated. • The adsorption and reduction mechanism was revealed by FTIR and XPS. - Abstract: Three-dimensional Fe-ethylene glycol (Fe-EG) complex microspheres were synthesized by a facile hydrothermal method, and were characterized by field emission scanning electron microscopy and transmission electron microscopy. The adsorption as well as reduction properties of the obtained Fe-EG complex microspheres towards Cr(VI) ions were studied. The experiment data of adsorption kinetic and isotherm were fitted by nonlinear regression approach. In neutral condition, the maximum adsorption capacity was 49.78 mg g{sup −1} at room temperature, and was increased with the increasing of temperature. Thermodynamic parameters including the Gibbs free energy, standard enthalpy and standard entropy revealed that adsorption of Cr(VI) was a feasible, spontaneous and endothermic process. Spectroscopic analysis revealed the adsorption of Cr(VI) was a physical adsorption process. The adsorbed CrO{sub 4}{sup 2−} ions were partly reduced to Cr(OH){sub 3} by Fe(II) ions and the organic groups in the Fe-EG complex.

  19. Chromium(III) Complex Obtained from Dipicolinic Acid: Synthesis, Characterization, X-Ray Crystal Structure and Electrochemical Studies

    Energy Technology Data Exchange (ETDEWEB)

    Ghasemi, Khaled; Rezvani, Ali Reza; Ghasemi, Fatemeh [Univ. of Sistan and Baluchestan, Zahedan (Iran, Islamic Republic of); Razak, Ibrahim Abdul; Rosli, Mohd Mustaqim [Universiti Sains Malaysia, Penang (Malaysia)

    2013-10-15

    The synthesis, X-ray crystallography, spectroscopic (IR, UV-vis), and electrochemical properties of the title compound, [H{sub 3}O][Cr(dipic){sub 2}] [H{sub 3}O{sup +}.Cl{sup -}] (1), (H{sub 2}dipic = 2,6-pyridinedicarboxylic acid), are reported. This complex crystallizes in the monoclinic space group Cc with a = 14.9006(10) A, b = 12.2114(8) A, c = 8.6337(6) A, α = 90.00 .deg., β = 92.7460(10) .deg., γ = 90.00 .deg., and V = 1569.16(18) A3 with Z = 4. The hydrogen bonding and noncovalent interactions play roles in the stabilization of the structure. In order to gain a better understanding of the most important geometrical parameters in the structure of the complex, atoms in molecules (AIM) method at B3LYP/6-31G level of theory has been employed.

  20. Redox Chemistry of Bis(pyrrolyl)pyridine Chromium and Molybdenum Complexes: An Experimental and Density Functional Theoretical Study.

    Science.gov (United States)

    Gowda, Anitha S; Petersen, Jeffrey L; Milsmann, Carsten

    2018-02-19

    The three- and four-membered redox series [Cr( Me PDP) 2 ] z (z = 1-, 2-, 3-) and [Mo( Me PDP) 2 ] z (z = 0, 1-, 2-, 3-) were synthesized to study the redox properties of the pincer ligand Me PDP 2- (H 2 Me PDP = 2,6-bis(5-methyl-3-phenyl-1H-pyrrol-2-yl)pyridine). The monoanionic complexes were characterized by X-ray crystallography, UV/vis/NIR spectroscopy, and magnetic susceptibility measurements. Experimental and density functional theory (DFT) studies are consistent with closed-shell Me PDP 2- ligands and +III oxidation states (d 3 , S = 3/2) for the central metal ions. Cyclic voltammetry established multiple reversible redox processes for [M( Me PDP) 2 ] 1- (M = Cr, Mo), which were further investigated via chemical oxidation and reduction. For molybdenum, one-electron oxidation yielded Mo( Me PDP) 2 which was characterized by X-ray crystallography, UV/vis/NIR, and magnetic susceptibility measurements. The experimental and computational data indicate metal-centered oxidation to a Mo IV complex (d 2 , S = 1) with two Me PDP 2- ligands. In contrast, one- and two-electron reductions were found to be ligand centered resulting in the formation of Me PDP •3- radicals, in which the unpaired electron is predominantly located on the central pyridine ring of the ligand. The presence of ligand radicals was established experimentally by observation of ligand-to-ligand intervalence charge transfer (LLIVCT) bands in the UV/vis/NIR spectra of the dianionic and trianionic complexes and further supported by broken-symmetry DFT calculations. X-ray crystallographic analyses of the one-electron-reduced species [M( Me PDP) 2 ] 2- (S = 1, M = Cr, Mo) established structural indicators for pincer reduction and showed localization of the radical on one of the two pincer ligands. The two-electron-reduced, trianionic complexes (S = 1/2) were characterized by UV/vis/NIR spectroscopy, magnetic susceptibility measurements, and EPR spectroscopy. The electronic structures of the reduced

  1. Hexavalent Chromium Compounds

    Science.gov (United States)

    Learn about chromium, exposure to which can increase your risk of lung cancer and cancer of the paranasal sinuses and nasal cavity. Hexavalent chromium compounds have been used as corrosion inhibitors in a wide variety of products and processes.

  2. Ballbot-type motion of N-heterocyclic carbenes on gold surfaces

    Science.gov (United States)

    Wang, Gaoqiang; Rühling, Andreas; Amirjalayer, Saeed; Knor, Marek; Ernst, Johannes Bruno; Richter, Christian; Gao, Hong-Jun; Timmer, Alexander; Gao, Hong-Ying; Doltsinis, Nikos L.; Glorius, Frank; Fuchs, Harald

    2017-02-01

    Recently, N-heterocyclic carbenes (NHCs) were introduced as alternative anchors for surface modifications and so offered many attractive features, which might render them superior to thiol-based systems. However, little effort has been made to investigate the self-organization process of NHCs on surfaces, an important aspect for the formation of self-assembled monolayers (SAMs), which requires molecular mobility. Based on investigations with scanning tunnelling microscopy and first-principles calculations, we provide an understanding of the microscopic mechanism behind the high mobility observed for NHCs. These NHCs extract a gold atom from the surface, which leads to the formation of an NHC-gold adatom complex that displays a high surface mobility by a ballbot-type motion. Together with their high desorption barrier this enables the formation of ordered and strongly bound SAMs. In addition, this mechanism allows a complementary surface-assisted synthesis of dimeric and hitherto unknown trimeric NHC gold complexes on the surface.

  3. Hexavalent Chromium Minimization Strategy

    Science.gov (United States)

    2011-05-01

    Logistics 4 Initiative - DoD Hexavalent Chromium Minimization Non- Chrome Primer IIEXAVAJ ENT CHRO:M I~UMI CHROMIUM (VII Oil CrfVli.J CANCEfl HAnRD CD...Management Office of the Secretary of Defense Hexavalent Chromium Minimization Strategy Report Documentation Page Form ApprovedOMB No. 0704-0188...00-2011 4. TITLE AND SUBTITLE Hexavalent Chromium Minimization Strategy 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6

  4. Heterogeneous chromium catalysts

    NARCIS (Netherlands)

    2005-01-01

    The present invention relates to a heterogeneous chromium catalyst system for the polymerisation of ethylene and/or alpha olefins prepared by the steps of: (a) providing a silica-containing support, (b) treating the silica-containing support with a chromium compound to form a chromium-based

  5. Carbenes and Nitrenes: Recent Developments in Fundamental Chemistry.

    Science.gov (United States)

    Wentrup, Curt

    2018-05-29

    There has been significant progress in the direct observation of carbenes, nitrenes, and many other reactive intermediates in recent years due to the application of matrix photolysis and flash vacuum pyrolysis linked with matrix isolation at cryogenic temperatures. Our understanding of singlet and triplet states has improved through the interplay of spectroscopy and computations. Bistable carbenes and nitrenes as well as many examples of tunneling have been discovered. Numerous rearrangements and fragmentations have been documented. This minireview aims to give an overview of some of these developments but will not generally cover laser flash photolysis and chemical reactions in liquid solution. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Adsorbate-driven cooling of carbene-based molecular junctions

    Czech Academy of Sciences Publication Activity Database

    Foti, Giuseppe; Vázquez, Héctor

    2017-01-01

    Roč. 8, Oct (2017), s. 2060-2068 ISSN 2190-4286 R&D Projects: GA ČR GA15-19672S EU Projects: European Commission(XE) 702114 - HEATEXMOL Institutional support: RVO:68378271 Keywords : adsorbate * carbene * current-induced heating and cooling * molecular junction * vibrations Subject RIV: BM - Solid Matter Physics ; Magnetism OBOR OECD: Condensed matter physics (including formerly solid state physics, supercond.) Impact factor: 3.127, year: 2016

  7. Catalytic Asymmetric C–H Insertions of Rhodium(II) Azavinyl Carbenes

    OpenAIRE

    Chuprakov, Stepan; Malik, Jamal A.; Zibinsky, Mikhail; Fokin, Valery V.

    2011-01-01

    A highly efficient enantioselective C–H insertion of azavinyl carbenes into unactivated alkanes has been developed. These transition metal carbenes are directly generated from readily available and stable 1-sulfonyl-1,2,3-triazoles in the presence of chiral Rh(II) carboxylates and are used for C–H functionalization of alkanes to access a variety of β-chiral sulfonamides.

  8. The Depolymerization of Poly(Ethylene Terephthalate) (PET) Using N-Heterocyclic Carbenes from Ionic Liquids

    Science.gov (United States)

    Kamber, Nahrain E.; Tsujii, Yasuhito; Keets, Kate; Waymouth, Robert M.; Pratt, Russell C.; Nyce, Gregory W.; Hedrick, James L.

    2010-01-01

    The depolymerization of the plastic polyethylene terephthalate (PET or PETE) is described in this laboratory procedure. The transesterification reaction used to depolymerize PET employs a highly efficient N-heterocyclic carbene catalyst derived from a commercially available imidazolium ionic liquid. N-heterocyclic carbenes are potent nucleophilic…

  9. Citric-acid preacidification enhanced electrokinetic remediation for removal of chromium from chromium-residue-contaminated soil.

    Science.gov (United States)

    Meng, Fansheng; Xue, Hao; Wang, Yeyao; Zheng, Binghui; Wang, Juling

    2018-02-01

    Electrokinetic experiments were conducted on chromium-residue-contaminated soils collected from a chemical plant in China. Acidification-electrokinetic remediation technology was proposed in order to solve the problem of removing inefficient with ordinary electrokinetic. The results showed that electrokinetic remediation removal efficiency of chromium from chromium-contaminated soil was significantly enhanced with acidizing pretreatment. The total chromium [Cr(T)] and hexavalent chromium [Cr(VI)] removal rate of the group acidized by citric acid (0.9 mol/L) for 5 days was increased from 6.23% and 19.01% in the acid-free experiments to 26.97% and 77.66% in the acidification-treated experiments, respectively. In addition, part of chromium with the state of carbonate-combined will be converted into water-soluble state through acidification to improve the removal efficiency. Within the appropriate concentration range, the higher concentration of acid was, the more chromium was released. So the removal efficiency of chromium depended on the acid concentration. The citric acid is also a kind of complexing agent, which produced complexation with Cr that was released by the electrokinetic treatment and then enhanced the removal efficiency. The major speciation of chromium that was removed from soils by acidification-electrokinetics remediation was acid-soluble speciation, revivification speciation and oxidation speciation, which reduced biological availability of chromium.

  10. C-N Bond Activation and Ring Opening of a Saturated N-Heterocyclic Carbene by Lateral Alkali-Metal-Mediated Metalation.

    Science.gov (United States)

    Hernán-Gómez, Alberto; Kennedy, Alan R; Hevia, Eva

    2017-06-01

    Combining alkali-metal-mediated metalation (AMMM) and N-heterocyclic carbene (NHC) chemistry, a novel C-N bond activation and ring-opening process is described for these increasingly important NHC molecules, which are generally considered robust ancillary ligands. Here, mechanistic investigations on reactions of saturated NHC SIMes (SIMes=[:C{N(2,4,6-Me 3 C 6 H 2 )CH 2 } 2 ]) with Group 1 alkyl bases suggest this destructive process is triggered by lateral metalation of the carbene. Exploiting co-complexation and trans-metal-trapping strategies with lower polarity organometallic reagents (Mg(CH 2 SiMe 3 ) 2 and Al(TMP)iBu 2 ), key intermediates in this process have been isolated and structurally defined. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Dirhodium(II Carbenes : The Chiral Product Cascade

    Directory of Open Access Journals (Sweden)

    Gregory H. P. Roos

    2000-12-01

    Full Text Available The last decade has witnessed enormous growth in the spectrum of highly efficient asymmetric synthetic transformations. One prominent example of this progress is the application of dirhodium (II carbenes generated from diazo- precursors. Innovative construction of ‘designer’ catalysts has played a integral role in extending the breadth of the synthetic cascade of non-racemic products now available through the range of cyclopropanation, C-X insertion, aromatic cycloaddition-rearrangement, and ylide-based reaction types. This review deals briefly with an overview of the important catalytic systems and maintains as its primary focus the cascade of diverse optically enriched products that flow from their applications.

  12. Effects of UV light and chromium ions on wood flavonoids

    International Nuclear Information System (INIS)

    Molnárné Hamvas, L.; Németh, K.; Stipta, J.

    2003-01-01

    The individual and simultaneous effect of UV light and chromium ions was investigated by spectrophotometric methods on inert surfaces impregnated with quercetin or robinetin. The UV-VIS spectra of the silica gel plates impregnated with these flavonoids were modified characteristically after irradiating ultraviolet light. Even a half an hour of irradiation has caused irreversible changes in the molecule structure. A certain chemical - presumably complexation - was concluded from the change of spectral bands assigned to flavonoids when impregnated with chromic ions. Hexavalent chromium caused more complex changes in the absorption spectra. The differences in the spectra could indicate either the oxidation and decomposition of flavonoids, or some kind of coordination process and the reduction of hexavalent chromium. The simultaneous application of UV light and chromium ions caused more pronounced effects. The complexation process between chromium(III) and flavonoid was completed

  13. Synthesis and electrochemical study of iron, chromium and tungsten aminocarbenes: Role of ligand structure and central metal nature

    Energy Technology Data Exchange (ETDEWEB)

    Hoskovcova, Irena [Department of Inorganic Chemistry, Institute of Chemical Technology, Technicka 5, 166 28 Prague 6 (Czech Republic); Rohacova, Jana; Dvorak, Dalimil; Tobrman, Tomas [Department of Organic Chemistry, Institute of Chemical Technology, Technicka 5, 166 28 Prague 6 (Czech Republic); Zalis, Stanislav [J. Heyrovsky Institute of Physical Chemistry, Academy of Science of the Czech Republic, Dolejskova 3, 182 23 Prague 8 (Czech Republic); Zverinova, Radka [Department of Inorganic Chemistry, Institute of Chemical Technology, Technicka 5, 166 28 Prague 6 (Czech Republic); J. Heyrovsky Institute of Physical Chemistry, Academy of Science of the Czech Republic, Dolejskova 3, 182 23 Prague 8 (Czech Republic); Ludvik, Jiri, E-mail: jiri.ludvik@jh-inst.cas.c [J. Heyrovsky Institute of Physical Chemistry, Academy of Science of the Czech Republic, Dolejskova 3, 182 23 Prague 8 (Czech Republic)

    2010-11-30

    Several series of Fischer-type aminocarbene complexes with central Fe, Cr or W atoms and with various carbene substitution were synthesized and electrochemically investigated by dc-polarography and cyclic voltammetry. The shifts and changes of reduction and oxidation potentials were evaluated using the linear free energy relationship (LFER) approach with respect to (a) the type of coordination, (b) the substitution on the carbene ligand and (c) the nature of the central metal atom. The analysis of measured data confirms that the reduction center is localized on the carbene moiety and is strongly influenced by both electronic and sterical properties of its substituents. The oxidation proceeds on the metal and depends mainly on its nature and on the {pi}-acidity of the ligands. Electrochemistry thus represents an important experimental approach to the description and understanding of the molecular electronic structure and redox properties. Experimental results are supported by DFT calculation of HOMO and LUMO orbitals shape and composition.

  14. Method for electrodeposition of nickel--chromium alloys and coating of uranium

    International Nuclear Information System (INIS)

    Stromatt, R.W.; Lundquist, J.R.

    1975-01-01

    High-quality electrodeposits of nickel-chromium binary alloys in which the percentage of chromium is controlled can be obtained by the addition of a complexing agent such as ethylenediaminetetraacetic disodium salt to the plating solution. The nickel-chromium alloys were found to provide an excellent hydrogen barrier for the protection of uranium fuel elements. (U.S.)

  15. Transition metal-induced activation of alkynes leading to metal carbene species: synthetic application to new {pi}-conjugated molecules

    Energy Technology Data Exchange (ETDEWEB)

    Abo, T; Ohe, K [Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510 (Japan)], E-mail: ohe@scl.kyoto-u.ac.jp

    2008-03-15

    The in situ generation of furylcarbene complexes by means of transition metals was applied to catalytic carbene reactions, such as Wittig-type olefination and cycloisomerization reactions. In the presence of [Rh(OAc){sub 2}]{sub 2} as a catalyst and triphenylphosphine as a carbene accepter, carbonyl-ene-ynes 1a reacted with benzaldehyde to give a 2-styrylfuran derivative 3a. The reaction involving phosphine-ylide formation followed by Wittig-type olefination with aldehydes was applied to synthesis of furfurylidene-containing p-extended conjugated molecules. A Ruthenium catalyst underwent cycloisomerization of 1,2-bis(carbonylenyl)acetylene 10a,b to afford 2,2'-bifuran structures. The crystal structure of 5,5'-diphenyl-2,2'-bifuran 11b was determined by X-ray crystallography. The ORTEP drawings of 11b exhibited transoid and highly planar structure. The emission bands of the bisfuran 11b were observed at 414 and 440 nm, its quantum yield (84%) was higher than that of a similar 5,5'-diphenyl-2,2'-bithiophene.

  16. Chromium carcinogenicity: California strategies.

    Science.gov (United States)

    Alexeeff, G V; Satin, K; Painter, P; Zeise, L; Popejoy, C; Murchison, G

    1989-10-01

    Hexavalent chromium was identified by California as a toxic air contaminant (TAC) in January 1986. The California Department of Health Services (CDHS) concurred with the findings of the International Agency for Research on Cancer that there is sufficient evidence to demonstrate the carcinogenicity of chromium in both animals and humans. CDHS did not find any compelling evidence demonstrating the existence of a threshold with respect to chromium carcinogenesis. Experimental data was judged inadequate to assess potential human reproductive risks from ambient exposures. Other health effects were not expected to occur at ambient levels. The theoretically increased lifetime carcinogenic risk from a continuous lifetime exposure to hexavalent chromium fell within the range 12-146 cancer cases per nanogram hexavalent chromium per cubic meter of air per million people exposed, depending on the potency estimate used. The primary sources found to contribute significantly to the risk of exposure were chrome platers, chromic acid anodizing facilities and cooling towers utilizing hexavalent chromium as a corrosion inhibitor. Evaluation of genotoxicity data, animal studies and epidemiological studies indicates that further consideration should be given to the potential carcinogenicity of hexavalent chromium via the oral route.

  17. A dual Lewis base activation strategy for enantioselective carbene-catalyzed annulations.

    Science.gov (United States)

    Izquierdo, Javier; Orue, Ane; Scheidt, Karl A

    2013-07-24

    A dual activation strategy integrating N-heterocyclic carbene (NHC) catalysis and a second Lewis base has been developed. NHC-bound homoenolate equivalents derived from α,β-unsaturated aldehydes combine with transient reactive o-quinone methides in an enantioselective formal [4 + 3] fashion to access 2-benzoxopinones. The overall approach provides a general blueprint for the integration of carbene catalysis with additional Lewis base activation modes.

  18. Substoichiometric extraction of chromium

    International Nuclear Information System (INIS)

    Shigematsu, T.; Kudo, K.

    1980-01-01

    Substoichiometric extraction of chromium with tetraphenylarsonium chloride (TPACl), tri-n-octylamine (TNOA), diethylammonium diethyldithiocarbamate (DDDC) and ammonium pyrrolidinedithiocarbamate (APDC) was examined in detail. Chromium can be extracted substoichiometrically in a pH range, which is 1.1-2.6 for the TPACl compound, 0.6-2.3 for the TNOA compound, 5.1-6.4 for the DDDC chelate and 3.9-4.9 for the APDC chelate. Chromium in high-purity calcium carbonate, Orchard Leaves (NBS SRM-1571) and Brewers Yeast (NBS SRM-1569) was determined by neutron activation analysis combined with substoichiometric extraction by DDDC and APDC. The values of 2.0+-0.02 ppm and 2.6+-0.2 ppm were obtained for Brewers Yeast and Orchard Leaves, respectively. These values were in good agreement with those reported by NBS. The reaction mechanism and the reaction ratio between hexavalent chromium and dithiocarbamate are also discussed. (author)

  19. Integrated Criteria Document Chromium

    NARCIS (Netherlands)

    Slooff W; Cleven RFMJ; Janus JA; van der Poel P; van Beelen P; Boumans LJM; Canton JH; Eerens HC; Krajnc EI; de Leeuw FAAM; Matthijsen AJCM; van de Meent D; van der Meulen A; Mohn GR; Wijland GC; de Bruijn PJ; van Keulen A; Verburgh JJ; van der Woerd KF

    1990-01-01

    Betreft de engelse versie van rapport 758701001
    Bij dit rapport behoort een appendix onder hetzelfde nummer getiteld: "Integrated Criteria Document Chromium: Effects" Auteurs: Janus JA; Krajnc EI
    (appendix: see 710401002A)

  20. Ru(II)-Catalyzed Cross-Coupling of Cyclopropenes with Diazo Compounds: Formation of Olefins from Two Different Carbene Precursors.

    Science.gov (United States)

    Wang, Bo; Yi, Heng; Zhang, Hang; Sun, Tong; Zhang, Yan; Wang, Jianbo

    2018-01-19

    Formal carbene dimerization is a convergent method for the synthesis of alkenes. Herein, we report a Ru(II)-catalyzed carbene dimerization of cyclopropenes and diazo compounds. The yields are up to 97% and the stereoselectivity are up to >20:1. Mechanistically, it has been experimentally demonstrated that the catalyst reacts with cyclopropene first to generate a Ru(II)-carbene species, which is attacked by nucleophilic diazo substrate, followed by dinitrogen extrusion to form the double bond.

  1. Zinc-Catalyzed Synthesis of Conjugated Dienoates through Unusual Cross-Couplings of Zinc Carbenes with Diazo Compounds.

    Science.gov (United States)

    Mata, Sergio; González, María J; González, Jesús; López, Luis A; Vicente, Rubén

    2017-01-23

    Zinc-catalyzed selective cross-coupling of two carbene sources, such as vinyl diazo compounds and enynones, enabled the synthesis of conjugated dienoate derivatives. This reaction involved the unprecedented coupling of a zinc furyl carbene with vinyl diazo compounds through the γ-carbon. Alternatively, dienoates were also prepared by a commutative cross-coupling of zinc vinyl carbenes generated from cyclopropenes and simple diazo compounds. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Nitrenes, carbenes, diradicals, and ylides. Interconversions of reactive intermediates.

    Science.gov (United States)

    Wentrup, Curt

    2011-06-21

    Rearrangements of aromatic and heteroaromatic nitrenes and carbenes can be initiated with either heat or light. The thermal reaction is typically induced by flash vacuum thermolysis, with isolation of the products at low temperatures. Photochemical experiments are conducted either under matrix isolation conditions or in solution at ambient temperature. These rearrangements are usually initiated by ring expansion of the nitrene or carbene to a seven-membered ring ketenimine, carbodiimide, or allene (that is, a cycloheptatetraene or an azacycloheptatetraene when a nitrogen is involved). Over the last few years, we have found that two types of ring opening take place as well. Type I is an ylidic ring opening that yields nitrile ylides or diazo compounds as transient intermediates. Type II ring opening produces either dienylnitrenes (for example, from 2-pyridylnitrenes) or 1,7-(1,5)-diradicals (such as those formed from 2-quinoxalinylnitrenes), depending on which of these species is better stabilized by resonance. In this Account, we describe our achievements in elucidating the nature of the ring-opened species and unraveling the connections between the various reactive intermediates. Both of these ring-opening reactions are found, at least in some cases, to dominate the subsequent chemistry. Examples include the formation of ring-opened ketenimines and carbodiimides, as well as the ring contraction reactions that form five-membered ring nitriles (such as 2- and 3-cyanopyrroles from pyridylnitrenes, N-cyanoimidazoles from 2-pyrazinyl and 4-pyrimidinylnitrenes, N-cyanopyrazoles from 2-pyrimidinylnitrenes and 3-pyridazinylnitrenes, and so forth). The mechanisms of formation of the open-chain and ring-contraction products were unknown at the onset of this study. In the course of our investigation, several reactions with three or more consecutive reactive intermediates have been unraveled, such as nitrene, seven-membered cyclic carbodiimide, and open-chain nitrile ylide

  3. Nitrene-carbene-carbene rearrangement. Photolysis and thermolysis of tetrazolo[5,1- a ]phthalazine with formation of 1-phthalazinylnitrene, o-cyanophenylcarbene, and phenylcyanocarbene

    DEFF Research Database (Denmark)

    Høj, Martin; Kvaskoff, David; Wentrup, Curt

    2014-01-01

    ). The rearrangement of 12 â., 13 â., 14 constitutes a carbene-carbene rearrangement. 1-Phthalazinylnitrene 310 is observed by means of its UV-vis spectrum in Ar matrix following FVT of 9 above 550 C. Rearrangement to cyanophenylcarbenes also takes place on FVT of 9 as evidenced by observation of the products of ring...... contraction, viz., fulvenallenes and ethynylcyclopentadienes 16-18. Thus the overall rearrangement 10 → 11 → 12 â., 13 â., 14 can be formulated. © 2013 American Chemical Society....

  4. Nanostructured Thin Films Obtained from Fischer Aminocarbene Complexes

    Directory of Open Access Journals (Sweden)

    Rosa E. Lazo-Jiménez

    2016-03-01

    Full Text Available The synthesis of four amphiphilic organometallic complexes with the general formula RC = M(CO5NH(CH215CH3, where R is a ferrocenyl 2(a-b or a phenyl 4(a-b group as a donor moiety and a Fischer carbene of chromium (0 or tungsten (0 as an acceptor group, are reported. These four push-pull systems formed Langmuir (L monolayers at the air-water interface, which were characterized by isotherms of surface pressure versus molecular area and compression/expansion cycles (hysteresis curves; Brewster angle microscopic images were also obtained. By using the Langmuir–Blodgett (LB method, molecular monolayers were transferred onto glass substrates forming Z-type multilayers. LB films were characterized through ultraviolet-visible spectroscopy, atomic force microscopy and X-ray diffraction techniques. Results indicated that films obtained from 2b complex [(Ferrocenyl(hexadecylaminemethylidene] pentacarbonyl tungsten (0 are the most stable and homogeneous; due to their properties, these materials may be incorporated into organic electronic devices.

  5. Nanostructured Thin Films Obtained from Fischer Aminocarbene Complexes

    Science.gov (United States)

    Lazo-Jiménez, Rosa E.; Ortega-Alfaro, M. Carmen; López-Cortés, José G.; Alvarez-Toledano, Cecilio; Chávez-Carvayar, José Á.; Ignés-Mullol, Jordi; González-Torres, Maykel; Carreón-Castro, Pilar

    2016-01-01

    The synthesis of four amphiphilic organometallic complexes with the general formula RC = M(CO)5NH(CH2)15CH3, where R is a ferrocenyl 2(a-b) or a phenyl 4(a-b) group as a donor moiety and a Fischer carbene of chromium (0) or tungsten (0) as an acceptor group, are reported. These four push-pull systems formed Langmuir (L) monolayers at the air-water interface, which were characterized by isotherms of surface pressure versus molecular area and compression/expansion cycles (hysteresis curves); Brewster angle microscopic images were also obtained. By using the Langmuir–Blodgett (LB) method, molecular monolayers were transferred onto glass substrates forming Z-type multilayers. LB films were characterized through ultraviolet-visible spectroscopy, atomic force microscopy and X-ray diffraction techniques. Results indicated that films obtained from 2b complex [(Ferrocenyl)(hexadecylamine)methylidene] pentacarbonyl tungsten (0) are the most stable and homogeneous; due to their properties, these materials may be incorporated into organic electronic devices. PMID:28773289

  6. Binding of molecular oxygen by an artificial heme analogue: investigation on the formation of an Fe–tetracarbene superoxo complex

    KAUST Repository

    Anneser, Markus R.; Haslinger, Stefan; Pö thig, Alexander; Cokoja, Mirza; D'Elia, Valerio; Hö gerl, Manuel P.; Basset, Jean-Marie; Kü hn, Fritz E.

    2016-01-01

    The dioxygen reactivity of a cyclic iron(II) tetra–NHC-complex (NHC: N-heterocyclic carbene) is investigated. Divergent oxidation behavior is observed depending on the choice of the solvent (acetonitrile or acetone). In the first case, exposure

  7. Formation of cyclobutanones by the photolytic reaction of (CO)/sub 5/Cr/double bond/C(OMe)Me with electron-rich olefins

    Energy Technology Data Exchange (ETDEWEB)

    Sierra, M.A.; Hegedus, L.S.

    1989-03-15

    Recent research has centered on the development of useful organic synthetic methodology based on the photolytic reactions of chromium Fischer carbene complexes, particularly in regards to the development of new /beta/-lactam syntheses. In the course of these studies it became evident that photolysis of chromium-carbene complexes resulted in the reversible production of chromium-ketene complexes, by a photochemically driven CO insertion into the chromium-carbene carbon double bond and that this unstable intermediate was responsible for /beta/-lactam formation.

  8. Facile insertion of a cyclic alkyl(amino) carbene carbon into the B-B bond of diboron(4) reagents.

    Science.gov (United States)

    Eichhorn, Antonius F; Kuehn, Laura; Marder, Todd B; Radius, Udo

    2017-10-24

    We report herein the room temperature insertion of the carbene carbon atom of the cyclic (alkyl)(amino) carbene cAAC Me into the B-B single bonds of the diboron(4) compounds B 2 pin 2 , B 2 cat 2 , B 2 neop 2 , and B 2 eg 2 (pin = pinacolato, cat = catecholato, neop = neopentylglycolato, eg = ethyleneglycolato).

  9. Reductive Coupling of Carbon Monoxide in a Rhenium Carbonyl Complex with Pendant Lewis Acids

    OpenAIRE

    Miller, Alexander J. M.; Labinger, Jay A.; Bercaw, John E.

    2008-01-01

    Phosphinoborane ligands impart unique reactivity to a rhenium carbonyl cation relative to simple phosphine complexes. Addition of either triethylborohydride or a platinum hydride (that can be formed from H2) forms a rhenium boroxycarbene. This carbene, which crystallizes as a dimer, disproportionates over a period of days to afford the starting cation and a structurally unprecedented boroxy(boroxymethyl)carbene, in which a new C−C bond has been formed between two reduced CO ligands. This prod...

  10. Environmental biochemistry of chromium.

    Science.gov (United States)

    Losi, M E; Amrhein, C; Frankenberger, W T

    1994-01-01

    Chromium is a d-block transitional element with many industrial uses. It occurs naturally in various crustal materials and is discharged to the environment as industrial waste. Although it can occur in a number of oxidation states, only 3+ and 6+ are found in environmental systems. The environmental behavior of Cr is largely a function of its oxidation state. Hexavalent Cr compounds (mainly chromates and dichromates) are considered toxic to a variety of terrestrial and aquatic organisms and are mobile in soil/water systems, much more so than trivalent Cr compounds. This is largely because of differing chemical properties: Hexavalent Cr compounds are strong oxidizers and highly soluble, while trivalent Cr compounds tend to form relatively inert precipitates at near-neutral pH. The trivalent state is generally considered to be the stable form in equilibrium with most soil/water systems. A diagram of the Cr cycle in soils and water is given in Fig. 6 (Bartlett 1991). This illustration provides a summary of environmentally relevant reactions. Beginning with hexavalent Cr that is released into the environment as industrial waste, there are a number of possible fates, including pollution of soil and surface water and leaching into groundwater, where it may remain stable and, in turn, can be taken up by plants or animals, and adsorption/precipitation, involving soil colloids and/or organic matter. Herein lies much of the environmental concern associated with the hexavalent form. A portion of the Cr(VI) will be reduced to the trivalent form by inorganic electron donors, such as Fe2+ and S2-, or by bioprocesses involving organic matter. Following this conversion, Cr3+ can be expected to precipitate as oxides and hydroxides or to form complexes with numerous ligands. This fraction includes a vast majority of global Cr reserves. Soluble Cr3+ complexes, such as those formed with citrate, can undergo oxidation when they come in contact with manganese dioxide, thus reforming

  11. Stabilized chromium oxide film

    Science.gov (United States)

    Garwin, Edward L.; Nyaiesh, Ali R.

    1988-01-01

    Stabilized air-oxidized chromium films deposited on high-power klystron ceramic windows and sleeves having a thickness between 20 and 150.ANG. are useful in lowering secondary electron emission yield and in avoiding multipactoring and window failure due to overheating. The ceramic substrate for the film is chosen from alumina, sapphire or beryllium oxide.

  12. Chromium and aging

    Science.gov (United States)

    Aging is associated with increased blood glucose, insulin, blood lipids, and fat mass, and decreased lean body mass leading to increased incidences of diabetes and cardiovascular diseases. Improved chromium nutrition is associated with improvements in all of these variables. Insulin sensitivity de...

  13. Carcinogenicity and mutagenicity of chromium.

    Science.gov (United States)

    Léonard, A; Lauwerys, R R

    1980-11-01

    Occupational exposure represents the main source of human contamination by chromium. For non-occupationally exposed people the major environmental exposure to chromium occurs as a consequence of its presence in food. Chromium must be considered as an essential element. Its deficiency impairs glucose metabolism. Trivalent chromium salts are poorly absorbed through the gastro-intestinal and respiratory tracts because they do not cross membranes easily. Hexavalent chromium can be absorbed by the oral and pulmonary routes and probably also through the skin. After its absorption, hexavalent chromium is rapidly reduced to the trivalent form which is probably the only form to be found in biological material. Epidemiological studies have shown that some chromium salts (mainly the slightly soluble hexavalent salts) are carcinogens. Lung cancers have, indeed, often been reported among workers in chromate-producing industry and, to a lesser extent, in workers from the chrome-pigment industry. The first attempts to produce cancers in experimental animals by inhalation or parenteral introduction gave negative or equivocal results but, from 1960, positive results have been obtained with various chromium compounds. As for the carcinogenic activity, the mutagenicity of chromium has mainly been found with hexavalent salts. In the majority of assay systems used, trivalent chromium appears inactive. It can be considered as evident, however, that the ultimate mutagen which binds to the genetic material is the trivalent form produced intracellularly from hexavalent chromium, the apparent lack of activity of the trivalent form being due to its poor cellular uptake.

  14. An unprecedented chemospecific and stereoselective tandem nucleophilic addition/cycloaddition reaction of nucleophilic carbenes with ketenimines.

    Science.gov (United States)

    Cheng, Ying; Ma, Yang-Guang; Wang, Xiao-Rong; Mo, Jun-Ming

    2009-01-16

    The first study of the reaction between nucleophilic carbenes and ketenimines is reported. The interaction of thiazole and benzothiazole carbenes with ketenimines proceeded in a chemospecific and stereoselective manner to produce thiazole- and benzothiazole-spiro-pyrrole derivatives generally in good yields. The reaction was proposed to proceed via a tandem nucleophilic addition of carbene to the C=N bond of ketenimine followed by a stepwise [3+2] cycloaddition of the 1,3-dipolar intermediate with the C=C bond of ketenimine. This reaction provides a powerful protocol for the construction of novel polyfunctional thiazole-spiro-pyrrole or benzothiazole-spiro-pyrrole compounds that are not readily accessible by other methods.

  15. Chemical functionalization of graphene by carbene cycloaddition: A density functional theory study

    International Nuclear Information System (INIS)

    Zan, Wenyan

    2014-01-01

    Graphical abstract: - Highlights: • The reaction process of graphene functionalization with CCl 2 group in atomic scales was studied. • The potential candidate carbenes CR 2 (R = H, F, CN, NO 2 0 , NO 2 90 , CH 3 , OCH 3 , CCH, C 6 H 5 ) were separately combined with graphene. • The functionalization of graphene nanoribbon with dichlorocarbene group was investigated. • The electronic properties of graphene functionalized by carbene groups were discussed. - Abstract: In this work, we have systematically studied the structural, energetic and electronic properties of graphene functionalized with carbene groups by using density functional theory. Introducing a low concentration of CCl 2 group in graphene was studied in detail by DFT, and closed cyclopropane-like three-membered ring structure was formed, meanwhile, the potential candidate carbene groups CR 2 (R = H, F, CH 3 , CN, NO 2 , OCH 3 , CCH, C 6 H 5 ) were added to graphene sheet, and CR 2 (R = H, NO 2 , CH 3 ) groups were expected to be good reactive species to covalently modify graphene. The graphene functionalization with carbene groups above can open graphene's band gap. More CCl 2 molecules were added to graphene, and different concentrations of CCl 2 group can tune graphene's band gap. In addition, the addition of CCl 2 group to graphene edges was investigated, and the stronger binding energy was found. Multiple CCl 2 molecules preferred to be bound with the same edge of graphene nanoribbon. This work provides an insight into the detailed molecular mechanism of graphene functionalization with carbene groups

  16. Immobilization of N-Heterocyclic Carbene Compounds: A Synthetic Perspective.

    Science.gov (United States)

    Zhong, Rui; Lindhorst, Anja C; Groche, Florian J; Kühn, Fritz E

    2017-02-08

    Over the course of the past 15 years the success story of N-heterocyclic carbene (NHC) compounds in organic, inorganic, and organometallic chemistry has been extended to another dimension. The immobilization of NHC compounds, undergoing continuous diversification, broadens their range of applications and leads to new solutions for challenges in catalytic and synthetic chemistry. This review intends to present a synthetic toolkit for the immobilization of NHC compounds, giving the reader an overview on synthetic techniques and strategies available in the literature. By individually summarizing and assessing the synthetic steps of the immobilization process, a comprehensive picture of the strategies and methodologies for the immobilization of NHC compounds is presented. Furthermore, the characterization of supported NHC compounds is discussed in detail in order to set up necessary criteria for an in-depth analysis of the immobilized derivatives. Finally, the catalytic applications of immobilized NHC compounds are briefly reviewed to illustrate the practical use of this technique for a broad variety of reaction types.

  17. Fullerene–Carbene Lewis Acid–Base Adducts

    KAUST Repository

    Li, Huaping

    2011-08-17

    The reaction between a bulky N-heterocylic carbene (NHC) and C60 leads to the formation of a thermally stable zwitterionic Lewis acid-base adduct that is connected via a C-C single bond. Low-energy absorption bands with weak oscillator strengths similar to those of n-doped fullerenes were observed for the product, consistent with a net transfer of electron density to the C60 core. Corroborating information was obtained using UV photoelectron spectroscopy, which revealed that the adduct has an ionization potential ∼1.5 eV lower than that of C60. Density functional theory calculations showed that the C-C bond is polarized, with a total charge of +0.84e located on the NHC framework and -0.84e delocalized on the C 60 cage. The combination of reactivity, characterization, and theoretical studies demonstrates that fullerenes can behave as Lewis acids that react with C-based Lewis bases and that the overall process describes n-doping via C-C bond formation. © 2011 American Chemical Society.

  18. Rhodium (II) carbene C-H insertion in water and catalyst reuse

    International Nuclear Information System (INIS)

    Candeias, Nuno R.; Gois, Pedro M.P.; Afonso, Carlos A.M.

    2007-01-01

    A five-session laboratory experiment is described for the synthesis of a beta-lactam via Rh(II) catalysed intramolecular C-H insertion of a alpha-diazo-alpha-ethoxycarbonyl acetamide. The metallo-carbene, responsible for the C-H bond activation, was generated from the diazo substrate and the catalyst Rh 2 (OAc) 4 . The high stability and solubility of the catalyst and the exclusive C-H insertion of the Rh-carbene allows the synthesis of this important heterocycle in water and the catalyst reutilization. (author)

  19. Tungsten(VI) Carbyne/Bis(carbene) Tautomerization Enabled by N-Donor SBA15 Surface Ligands: A Solid-State NMR and DFT Study

    KAUST Repository

    Bendjeriou-Sedjerari, Anissa

    2016-08-11

    Designing supported well-defined bis(carbene) complexes remains a key challenge in heterogeneous catalysis. The reaction of W(CtBu)(CH(2)tBu)(3) with amine-modified mesoporous SBA15 silica, which has vicinal silanol/silylamine pairs [(SiOH)(SiNH2)], leads to [(SiNH2-)(SiO-)W(CHtBu)(CH(2)tBu)(2)] and [(SiNH2-)(SiO-)W(=CHtBu)(2)(CH(2)tBu). Variable temperature, H-1-H-1 2D double-quantum, H-1-C-13 HETCOR, and HETCOR with spin diffusion solid-state NMR spectroscopy demonstrate tautomerization between the alkyl alkylidyne and the bis(alkylidene) on the SBA15 surface. Such equilibrium is possible through the coordination of W to the surface [(Si-OH)(Si-NH2)] groups, which act as a [N,O] pincer ligand. DFT calculations provide a rationalization for the surface-complex tautomerization and support the experimental results. This direct observation of such a process shows the strong similarity between molecular mechanisms in homogeneous and heterogeneous catalysis. In propane metathesis (at 150 degrees C), the tungsten bis(carbene) tautomer is favorable, with a turnover number (TON) of 262. It is the highest TON among all the tungsten alkyl-supported catalysts.

  20. Tungsten(VI) Carbyne/Bis(carbene) Tautomerization Enabled by N-Donor SBA15 Surface Ligands: A Solid-State NMR and DFT Study

    KAUST Repository

    Bendjeriou-Sedjerari, Anissa; Sofack-Kreutzer, Julien; Minenkov, Yury; Abou-Hamad, Edy; Hamzaoui, Bilel; Werghi, Baraa; Anjum, Dalaver H.; Cavallo, Luigi; Huang, Kuo-Wei; Basset, Jean-Marie

    2016-01-01

    Designing supported well-defined bis(carbene) complexes remains a key challenge in heterogeneous catalysis. The reaction of W(CtBu)(CH(2)tBu)(3) with amine-modified mesoporous SBA15 silica, which has vicinal silanol/silylamine pairs [(SiOH)(SiNH2)], leads to [(SiNH2-)(SiO-)W(CHtBu)(CH(2)tBu)(2)] and [(SiNH2-)(SiO-)W(=CHtBu)(2)(CH(2)tBu). Variable temperature, H-1-H-1 2D double-quantum, H-1-C-13 HETCOR, and HETCOR with spin diffusion solid-state NMR spectroscopy demonstrate tautomerization between the alkyl alkylidyne and the bis(alkylidene) on the SBA15 surface. Such equilibrium is possible through the coordination of W to the surface [(Si-OH)(Si-NH2)] groups, which act as a [N,O] pincer ligand. DFT calculations provide a rationalization for the surface-complex tautomerization and support the experimental results. This direct observation of such a process shows the strong similarity between molecular mechanisms in homogeneous and heterogeneous catalysis. In propane metathesis (at 150 degrees C), the tungsten bis(carbene) tautomer is favorable, with a turnover number (TON) of 262. It is the highest TON among all the tungsten alkyl-supported catalysts.

  1. Comparative reactivity of different types of stable cyclic and acyclic mono- and diamino carbenes with simple organic substrates.

    Science.gov (United States)

    Martin, David; Canac, Yves; Lavallo, Vincent; Bertrand, Guy

    2014-04-02

    A series of stable carbenes, featuring a broad range of electronic properties, were reacted with simple organic substrates. The N,N-dimesityl imidazolylidene (NHC) does not react with isocyanides, whereas anti-Bredt di(amino)carbene (pyr-NHC), cyclic (alkyl)(amino)carbene (CAAC), acyclic di(amino)carbene (ADAC), and acyclic (alkyl)(amino)carbene (AAAC) give rise to the corresponding ketenimines. NHCs are known to promote the benzoin condensation, and we found that the CAAC, pyr-NHC, and ADAC react with benzaldehyde to give the ketone tautomer of the Breslow intermediate, whereas the AAAC first gives the corresponding epoxide and ultimately the Breslow intermediate, which can be isolated. Addition of excess benzaldehyde to the latter does not lead to benzoin but to a stable 1,3-dioxolane. Depending on the electronic properties of carbenes, different products are also obtained with methyl acrylate as a substrate. The critical role of the carbene electrophilicity on the outcome of reactions is discussed.

  2. Voltammetric investigation of the distribution of hydroxo-, chloro-, edta and carbohydrate complexes of lead, chromium, zinc, cadmium and copper: Potential application to metal speciation studies in brewery wastewater

    Directory of Open Access Journals (Sweden)

    J. Catherine Ngila

    2005-06-01

    Full Text Available This paper reports results on complex formation reactions between OH-, Cl-, EDTA and carbohydrate ligands with Pb2+ ions at various [LT]:[MT] ratios and at different pH values (1.5-13.0. Differential pulse anodic stripping voltammetry (DPASV employing an ex situ plated thin mercury film electrode (TMFE was used to measure the shifts in peak potentials. Formation of simple, polyligand as well as mixed ligand complexes are reported. The reactions between the Pb(II and the carbohydrate ligands showed pronounced pH dependency on metal forms compared to reactions with simple inorganic ions such as chloride. Modeling of the experimental data obtained with the DPASV method was done using computer software (3D-VISE. The calculated complex formation curves (CCFC based on mass balance equations were fitted to the experimental complex formation curves (ECFC and the goodness of the fit evaluated (RSD < 5%. These studies were applied to Pb, Cr, Zn, Cd and Cu speciation in brewery wastewater in which differences between total metal determined by flame atomic absorption spectrometry (FAAS after acid digestion and labile fraction determined by DPASV were used to estimate the percentage of non-labile fraction (mainly metal-organic complexes. Up to 90% of the metal was found to exist as the “inert” fraction, implying that the effluent system from the brewery industry poses minimal health risks to the environment with regard to toxic forms of the metals as the organically bound metal forms are generally known to have low toxicity compared to the aquo or labile metal forms.

  3. Probing protein surface with a solvent mimetic carbene coupled to detection by mass spectrometry.

    Science.gov (United States)

    Gómez, Gabriela E; Mundo, Mariana R; Craig, Patricio O; Delfino, José M

    2012-01-01

    Much knowledge into protein folding, ligand binding, and complex formation can be derived from the examination of the nature and size of the accessible surface area (SASA) of the polypeptide chain, a key parameter in protein science not directly measurable in an experimental fashion. To this end, an ideal chemical approach should aim at exerting solvent mimicry and achieving minimal selectivity to probe the protein surface regardless of its chemical nature. The choice of the photoreagent diazirine to fulfill these goals arises from its size comparable to water and from being a convenient source of the extremely reactive methylene carbene (:CH(2)). The ensuing methylation depends primarily on the solvent accessibility of the polypeptide chain, turning it into a valuable signal to address experimentally the measurement of SASA in proteins. The superb sensitivity and high resolution of modern mass spectrometry techniques allows us to derive a quantitative signal proportional to the extent of modification (EM) of the sample. Thus, diazirine labeling coupled to electrospray mass spectrometry (ESI-MS) detection can shed light on conformational features of the native as well as non-native states, not easily addressable by other methods. Enzymatic fragmentation of the polypeptide chain at the level of small peptides allows us to locate the covalent tag along the amino acid sequence, therefore enabling the construction of a map of solvent accessibility. Moreover, by subsequent MS/MS analysis of peptides, we demonstrate here the feasibility of attaining amino acid resolution in defining the target sites. © American Society for Mass Spectrometry, 2011

  4. Role of β-h elimination in rhodium-mediated carbene insertion polymerization

    NARCIS (Netherlands)

    Finger, M.; Reek, J.N.H.; de Bruin, B.

    2011-01-01

    The importance of β-H elimination as a possible mechanism to induce chain termination/transfer and/or the formation of stereodefects in the Rh(diene)-mediated oligomerization and polymerization of carbenes has been studied by means of different approaches. As a remarkable feature, this reaction is

  5. Enantioselective [3+3] atroposelective annulation catalyzed by N-heterocyclic carbenes

    KAUST Repository

    Zhao, Changgui; Guo, Donghui; Munkerup, Kristin; Huang, Kuo-Wei; Li, Fangyi; Wang, Jian

    2018-01-01

    on the transition-metal-catalyzed transformations. Here, we report the enantioselective NHC-catalyzed (NHC: N-heterocyclic carbenes) atroposelective annulation of cyclic 1,3-diones with ynals. In the presence of NHC precatalyst, base, Lewis acid and oxidant, a

  6. Mechanistic Investigation of the Ruthenium–N-Heterocyclic-Carbene-Catalyzed Amidation of Alcohols and Amines

    DEFF Research Database (Denmark)

    Makarov, Ilya; Fristrup, Peter; Madsen, Robert

    2012-01-01

    The mechanism of the ruthenium–N-heterocyclic-carbene-catalyzed formation of amides from alcohols and amines was investigated by experimental techniques (Hammett studies, kinetic isotope effects) and by a computational study by using dispersion-corrected density functional theory (DFT/ M06...

  7. Synthesis, crystal structure, antimicrobial activity and electrochemistry study of chromium(III) and copper(II) complexes based on semicarbazone Schiff base and azide ligands

    Czech Academy of Sciences Publication Activity Database

    Shaabani, B.; Khandar, A.A.; Dušek, Michal; Pojarová, Michaela; Mahmoudi, F.

    2013-01-01

    Roč. 394, JAN (2013), s. 563-568 ISSN 0020-1693 Grant - others:AV ČR(CZ) AP0701 Program:Akademická prémie - Praemium Academiae Institutional support: RVO:68378271 Keywords : antimicrobial activity * azide ligand * metal complex * Schiff base ligand * X-ray structure Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.041, year: 2013

  8. Diphenylcarbene Protected by Four ortho-Iodine Groups: An Unusually Persistent Triplet Carbene

    Directory of Open Access Journals (Sweden)

    Katsuyuki Hirai

    2016-11-01

    Full Text Available Diphenyldiazomethane with four iodine groups at the ortho positions and two tert-butyl groups at the para positions, i.e., bis(4-tert-butyl-2,6-diiodophenyldiazomethane (1a-N2, was synthesized as a sterically hindered triplet carbene precursor. Irradiation of 1a-N2 in solution effectively generated the corresponding triplet diphenylcarbene 31a, which was characterized by UV-vis spectroscopy at low temperature, along with laser flash photolysis techniques at room temperature. The UV-vis spectrum of 31a was obtained by irradiating 1a-N2 in a 2-methyltetrahydrofuran matrix at 77 K. The ESR spectrum showed no triplet carbene signals, while a radical species was observed at the anticipated temperature of the decomposition of triplet carbene 31a. Transient absorption bands ascribable to 31a were observed by laser flash photolysis of 1a-N2 in a degassed benzene solution and decayed very slowly with a second-order rate constant (2k/εl of 5.5 × 10−3·s−1. Steady-state irradiation of 1a-N2 in degassed benzene afforded 9,10-diarylphenanthrene derivative 2a in a 31% yield. Triplet carbene 31a was also trapped by either oxygen (kO2 = 6.5 × 105 M−1·s−1 or 1,4-cyclohexadiene (kCHD = 1.5 M−1·s−1 to afford the corresponding ketone 1a-O or the diarylmethane 1a-H2. The carbene was shown to be much less reactive than the triplet diphenylcarbene that is protected by two ortho-iodo and two ortho-bromo groups, 31b.

  9. Progress in the chemistry of chromium(V) doping agents used in polarized target materials

    International Nuclear Information System (INIS)

    Krumpolc, M.; Hill, D.; Struhrmann, H.B.

    1990-01-01

    We wish to report progress in two areas of the chromium (V)-based doping agents: Two commonly used chromium (V) complexes, I and II, have been synthesized in perdeuterated form (i.e., all hydrogens replaced by deuterium). They are sodium bis(2-ethyl-2-deuteroxy-butyrato)oxochromate(V)monodeuterate, IV, (acronym EDBA-Cr(V)), and sodium bis(2-deuteroxy-2-methylpropionato)oxochromate(V), III, (acronym DMPA-Cr(V)). A synthetic route leading to the preparation of stable, chromium(III)-free solutions of chromium(V) in diols (1,2-ethanediol/ethylene glycol/and 1,2-propanediol/propylene glycol/) has been outlined

  10. Selenophene transition metal complexes

    Energy Technology Data Exchange (ETDEWEB)

    White, Carter James [Iowa State Univ., Ames, IA (United States)

    1994-07-27

    This research shows that selenophene transition metal complexes have a chemistry that is similar to their thiophene analogs. Selenophene coordination has been demonstrated and confirmed by molecular structure in both the η5- and the η1(Se)-coordination modes. The reaction chemistry of selenophene complexes closely resembles that of the analogous thiophene complexes. One major difference, however, is that selenophene is a better donor ligand than thiophene making the selenophene complexes more stable than the corresponding thiophene complexes. The 77Se NMR chemical shift values for selenophene complexes fall within distinct regions primarily depending on the coordination mode of the selenophene ligand. In the final paper, the C-H bond activation of η1(S)-bound thiophenes, η1(S)-benzothiophene and η1(Se)-bound selenophenes has been demonstrated. The deprotonation and rearrangement of the η1(E)-bound ligand to the carbon bound L-yl complex readily occurs in the presence of base. Reprotonation with a strong acid gives a carbene complex that is unreactive towards nucleophilic attack at the carbene carbon and is stable towards exposure to air. The molecular structure of [Cp(NO)(PPh3)Re(2-benzothioenylcarbene)]O3SCF3 was determined and contains a Re-C bond with substantial double bond character. Methyl substitution for the thienylcarbene or selenylcarbene gives a carbene that rearranges thermally to give back the η1(E)-bound complex. Based on these model reactions, a new mechanism for the H/D exchange of thiophene over the hydrodesulfurization catalyst has been proposed.

  11. Determination of Chromium(III) Picolinate Using High Performance Liquid Chromatography-Ultraviolet Spectrophotometry

    International Nuclear Information System (INIS)

    Kim, Sung Il; Woo, Dong Jin; Kang, Dae Kyung; Lee, Myung Hee; Woo, Gun Jo; Cha, Ki Won

    2003-01-01

    Cr-(pic) 3 has been widely used as food additives, drugs, and feed additives. Accordingly, its determination method should be established. In the present paper, we have studied the determination method of chromium(III) picolinate accurately using ESI-MS on-lined with HPLC. Chromium(III) picolinate in feed products was determined successfully. Chromium(III) is very well known as an essential mineral. It is suggested as a cofactor in the maintenance of both normal lipid and carbohydrate metabolism by assisting the action of insulin on a cell membrane. According to the National Research Council, the daily recommended intake of chromium(III) is 50-200 μg. Several organic chromium(III) complexes have been reported to have significantly higher absorption and tissue incorporation activity than inorganic salts such as chromium(III) chloride

  12. Adsorption and desorption of hydrolyzed metal ions. 3. Scandium and chromium

    International Nuclear Information System (INIS)

    Gray, B.; Matijevic, E.; Clarkson Univ., Potsdam, NY

    1987-01-01

    Adsorption of scandium(III) and chromium(III) species on a PVC latex was measured using radioactive isotopes; the uptake increased with increasing pH. The data were interpreted by combining aspects of the models of James and Healy and also of Anderson and Bockris. The experimental and calculated results agree quite well for scandium, but not for chromium. The deviation in the latter case is believed to be due to polymerization of the hydrolyzed chromium cations and to the interaction of chromium with the anionic surface groups of the latex. Neither of these interactions occur with scandium. Hydrolyzed scandium species adsorbed on the latex were removed by acidifying the dispersion, while chromium complexes were not, substantiating the proposed difference in the chemical nature of chromium and scandium species at the solid/solution interface. 32 refs.; 8 figs.; 8 tabs

  13. Dietary Chromium Supplementation for Targeted Treatment of Diabetes Patients with Comorbid Depression and Binge Eating

    Science.gov (United States)

    Brownley, Kimberly A.; Boettiger, Charlotte A.; Young, Laura; Cefalu, William T.

    2015-01-01

    Dietary chromium supplementation for the treatment of diabetes remains controversial. The prevailing view that chromium supplementation for glucose regulation is unjustified has been based upon prior studies showing mixed, modest-sized effects in patients with type 2 diabetes (T2DM). Based on chromium's potential to improve insulin, dopamine, and serotonin function, we hypothesize that chromium has a greater glucoregulatory effect in individuals who have concurrent disturbances in dopamine and serotonin function – that is, complex patients with comorbid diabetes, depression, and binge eating. We propose, as suggested by the collective data to date, the need to go beyond the “one size fits all” approach to chromium supplementation and put forth a series of experiments designed to link physiological and neurobehavioral processes in the chromium response phenotype. PMID:25838140

  14. Hexavalent Chromium Substitution Projects

    Science.gov (United States)

    2011-05-12

    Hexavalent Chromium Substitution Projects Date (12 May 2011) Gene McKinley ASC/WNV (937) 255-3596 Gene.McKinley@wpafb.af.mil Aeronautical Systems...valid OMB control number. 1. REPORT DATE 12 MAY 2011 2. REPORT TYPE 3. DATES COVERED 00-00-2011 to 00-00-2011 4. TITLE AND SUBTITLE Hexavalent ...A-10) – AETC (T-6, T-38 and T1A) • Both Cr Primers & Non-Cr primers as well as Cr Surface Treatment – F-22 8 Non- Chrome Tie-coat & touch-up

  15. Biosorption and biotransformation of chromium by Serratia sp. isolated from tannery effluent.

    Science.gov (United States)

    Srivastava, Shaili; Thakur, Indu Shekhar

    2012-01-01

    A bacterium isolated from soil and sediment ofa leather tanning mill's effluent was identified as Serratia sp. by the analysis of 16S rDNA. Scanning electron microscopy-energy dispersive X-ray analysis (SEM-EDX) and transmission electron microscopy (TEM) were used to assess morphological changes and confirm chromium biosorption in Serratia sp. both in a shake-flask culture containing chromium and in a tannery wastewater. The SEMEDX and the elemental analysis of the chromate-containing samples confirmed the binding of chromium with the bacterial biomass. The TEM exhibited chromium accumulation throughout the bacterial cell, with some granular deposits in the cell periphery and in the cytoplasm. X-ray diffraction analysis (XRD) was used to quantify the chromium and to determine the chemical nature of the metal-microbe interaction. The XRD data showed the crystalline character of the precipitates, which consisted of mainly calcium chromium oxide, chromium fluoride phosphate and related organo-Cr(III) complex crystals. The XRD data also revealed a strong involvement of cellular carboxyl and phosphate groups in chromium binding by the bacterial biomass. The results of the study indicated that a combined mechanism of ion-exchange, complexation, croprecipitation and immobilization was involved in the biosorption of chromium by bacterial cells in contaminated environments.

  16. Carcinogenicity of chromium and chemoprevention: a brief update

    Directory of Open Access Journals (Sweden)

    Wang Y

    2017-08-01

    Full Text Available Yafei Wang,1,* Hong Su,1,* Yuanliang Gu,1 Xin Song,1 Jinshun Zhao1,2 1Department of Preventative Medicine, Zhejiang Key Laboratory of Pathophysiology, School of Medicine, Ningbo University, Ningbo, People’s Republic of China; 2Toxicology and Molecular Biology Branch, Health Effects Laboratory Division, National Institute for Occupational Safety and Health, Morgantown, WV, USA *These authors contributed equally to this work Abstract: Chromium has two main valence states: hexavalent chromium (Cr[VI] and trivalent chromium (Cr[III]. Cr(VI, a well-established human carcinogen, can enter cells by way of a sulfate/phosphate anion-transport system, and then be reduced to lower-valence intermediates consisting of pentavalent chromium (Cr[V], tetravalent chromium (Cr[IV] or Cr(III via cellular reductants. These intermediates may directly or indirectly result in DNA damage or DNA–protein cross-links. Although Cr(III complexes cannot pass easily through cell membranes, they have the ability to accumulate around cells to induce cell-surface morphological alteration and result in cell-membrane lipid injuries via disruption of cellular functions and integrity, and finally to cause DNA damage. In recent years, more research, including in vitro, in vivo, and epidemiological studies, has been conducted to evaluate the genotoxicity/carcinogenicity induced by Cr(VI and/or Cr(III compounds. At the same time, various therapeutic agents, especially antioxidants, have been explored through in vitro and in vivo studies for preventing chromium-induced genotoxicity/carcinogenesis. This review aims to provide a brief update on the carcinogenicity of Cr(VI and Cr(III and chemoprevention with different antioxidants. Keywords: hexavalent chromium, Cr(VI, trivalent chromium, Cr(III, genotoxicity, carcinogenicity, chemoprevention, antioxidant 

  17. Steric and electronic parameters of a bulky yet flexible N-heterocyclic carbene: 1,3-bis(2,6-bis(1-ethylpropyl)phenyl)imidazol-2-ylidene (IPent)

    KAUST Repository

    Collado, Alba; Balogh, Já nos; Meiries, Sé bastien; Slawin, Alexandra M. Z.; Falivene, Laura; Cavallo, Luigi; Nolan, Steven P.

    2013-01-01

    The free N-heterocyclic carbene IPent (1; IPent = 1,3-bis(2,6-bis(1- ethylpropyl)phenyl)imidazol-2-ylidene) was prepared from the corresponding imidazolium chloride salt (2). The steric and electronic parameters of 1 were determined by synthesis of the gold(I) chloride complex [Au(IPent)Cl] (3) and the nickel-carbonyl complex [Ni(IPent)(CO)3] (4), respectively. 3 and 4 were fully characterized by NMR spectroscopy, elemental analysis, and X-ray diffraction studies on single crystals. © 2013 American Chemical Society.

  18. Steric and electronic parameters of a bulky yet flexible N-heterocyclic carbene: 1,3-bis(2,6-bis(1-ethylpropyl)phenyl)imidazol-2-ylidene (IPent)

    KAUST Repository

    Collado, Alba

    2013-06-10

    The free N-heterocyclic carbene IPent (1; IPent = 1,3-bis(2,6-bis(1- ethylpropyl)phenyl)imidazol-2-ylidene) was prepared from the corresponding imidazolium chloride salt (2). The steric and electronic parameters of 1 were determined by synthesis of the gold(I) chloride complex [Au(IPent)Cl] (3) and the nickel-carbonyl complex [Ni(IPent)(CO)3] (4), respectively. 3 and 4 were fully characterized by NMR spectroscopy, elemental analysis, and X-ray diffraction studies on single crystals. © 2013 American Chemical Society.

  19. Chromium in Postmortem Material.

    Science.gov (United States)

    Dudek-Adamska, Danuta; Lech, Teresa; Konopka, Tomasz; Kościelniak, Paweł

    2018-04-17

    Recently, considerable attention has been paid to the negative effects caused by the presence and constant increase in concentration of heavy metals in the environment, as well as to the determination of their content in human biological samples. In this paper, the concentration of chromium in samples of blood and internal organs collected at autopsy from 21 female and 39 male non-occupationally exposed subjects is presented. Elemental analysis was carried out by an electrothermal atomic absorption spectrometer after microwave-assisted acid digestion. Reference ranges of chromium in the blood, brain, stomach, liver, kidneys, lungs, and heart (wet weight) in the population of Southern Poland were found to be 0.11-16.4 ng/mL, 4.7-136 ng/g, 6.1-76.4 ng/g, 11-506 ng/g, 2.9-298 ng/g, 13-798 ng/g, and 3.6-320 ng/g, respectively.

  20. Role of paramagnetic chromium in chromium(VI)-induced damage in cultured mammalian cells.

    OpenAIRE

    Sugiyama, M

    1994-01-01

    Chromium(VI) compounds are known to be potent toxic and carcinogenic agents. Because chromium(VI) is easily taken up by cells and is subsequently reduced to chromium(III), the formation of paramagnetic chromium such as chromium(V) and chromium(III) is believed to play a role in the adverse biological effects of chromium(VI) compounds. The present report, uses electron spin resonance (ESR) spectroscopy; the importance of the role of paramagnetic chromium in chromium(VI)-induced damage in intac...

  1. Specification for corrosion-resisting chromium and chromium-nickel steel covered welding electrodes

    International Nuclear Information System (INIS)

    Anon.

    1981-01-01

    This specification prescribes requirements for covered corrosion-resisting chromium and chromium-nickel steel electrodes. These electrodes are normally used for shielded metal arc welding, and include those alloy steels designated as corrosion or heat-resisting chromium and chromium-nickel steels, in which chromium exceeds 4.0% and nickel does not exceed 50.0%

  2. Specification for corrosion-resisting chromium and chromium-nickel steel covered welding electrodes

    International Nuclear Information System (INIS)

    Anon.

    1981-01-01

    This specification prescribes requirements for covered corrosion-resisting chromium and chromium-nickel steel electrodes. These electrodes are normally used for shielded metal arc welding, and include those alloy steels designated as corrosion or heat-resisting chromium and chromium-nickel steels, in which chromium exceeds 4.0 percent and nickel does not exceed 50.0 percent

  3. Asymmetric Reduction of tert-Butanesulfinyl Ketimines by N-Heterocyclic Carbene Boranes.

    Science.gov (United States)

    Liu, Tao; Chen, Ling-yan; Sun, Zhihua

    2015-11-20

    N-heterocyclic carbene borane (NHC-borane) based on a triazole core is demonstrated for the first time to be efficient for reduction of a variety of tert-butanesulfinyl ketimines. Up to 95% yield and up to >99% diastereomeric excess were achieved. NHC-borane exhibited excellent activities that are more efficient than or comparable to commonly used reductive reagents such as NaBH4, NaBH3CN, l-selectride, Ru catalyst, or BH3-THF.

  4. Bimacrocyclic concave N-heterocyclic carbenes (NHCs): synthesis, structure, and application in catalyses

    OpenAIRE

    Lüning , Ulrich; Winkelmann , Ole

    2009-01-01

    Abstract Imidazolinium moieties have been incorporated into bimacrocycles to generate precursors for concave N-heterocyclic carbenes (NHCs). Starting from 2-nitroresorcinol and alkenols, symmetric concave imidazolinium salts 1 were obtained. Bimacrocyclization was achieved via ring closing metathesis (RCM). In an analogous fashion, axially chiral concave imidazolinium salts 2 were obtained by using a naphthalene bridgehead devoid of local C2-symmetry. The concave NHCs derived from ...

  5. Tip-induced gating of molecular levels in carbene-based junctions

    Czech Academy of Sciences Publication Activity Database

    Foti, Giuseppe; Vázquez, Héctor

    2016-01-01

    Roč. 27, č. 12 (2016), 1-8, č. článku 125702. ISSN 0957-4484 R&D Projects: GA ČR GA15-19672S Institutional support: RVO:68378271 Keywords : single molecule transport * N-heterocyclic carbene * tip-induced gating * DFT-NEGF * metal-molecule charge rearrangement Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.440, year: 2016

  6. Divergent Reactivity of Rhodium(I) Carbenes Derived from Indole Annulations.

    Science.gov (United States)

    Li, Xiaoxun; Li, Hui; Song, Wangze; Tseng, Po-Sen; Liu, Lingyan; Guzei, Ilia A; Tang, Weiping

    2015-10-26

    Rhodium(I) carbenes were generated from propargylic alcohol derivatives as the result of a dehydrative indole annulation. Depending on the choice of the electron-withdrawing group on the aniline nitrogen nucleophile, either a cyclopropanation product or dimerization product was obtained chemoselectively. Intramolecular hydroamidation occurred for the same type of propargylic alcohol derivatives when other transition-metal catalysts were employed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Reduction of the Work Function of Gold by N-Heterocyclic Carbenes

    KAUST Repository

    Kim, Hye Kyung

    2017-04-12

    N-Heterocyclic carbenes (NHCs) bind strongly to gold and other metals. This work experimentally probes the effect of NHCs on the work function (WF) of gold for the first time, theoretically analyzes the origin of this effect, and examines the effectiveness of NHC-modified gold as an electron-injecting electrode. UV photoelectron spectroscopy shows the WF of planar gold is reduced by nearly 2 eV to values of 3.3–3.5 eV. This effect is seen for NHCs with various heterocyclic cores, and with either small or large N,N′-substituents. DFT calculations indicate the WF reduction results from both the interface dipole formed between the NHC and the gold and from the NHC molecular dipole. For N,N′-diisopropyl-NHCs, an important contributor to the former is charge transfer associated with coordination of the carbene carbon atom to gold. In contrast, the carbene carbon of N,N′-2,6-diisopropylphenyl-NHCs is not covalently bound to gold, resulting in a lower interface dipole; however, a larger molecular dipole partially compensates for this. Single-layer C60 diodes with NHC-modified gold as the bottom electrode demonstrate high rectification ratios and show that these electrodes can act as effective electron-injecting contacts, suggesting they may be useful for a variety of materials applications.

  8. Masked N-Heterocyclic Carbene-Catalyzed Alkylation of Phenols with Organic Carbonates.

    Science.gov (United States)

    Lui, Matthew Y; Yuen, Alexander K L; Masters, Anthony F; Maschmeyer, Thomas

    2016-09-08

    An easily prepared masked N-heterocyclic carbene, 1,3-dimethylimidazolium-2-carboxylate (DMI-CO2 ), was investigated as a "green" and inexpensive organocatalyst for the alkylation of phenols. The process made use of various low-toxicity and renewable alkylating agents, such as dimethyl- and diethyl carbonate, in a focused microwave reactor. DMI-CO2 was found to be a very active catalyst and excellent yields of a range of aryl alkyl ethers were obtained under relatively benign conditions. The observed difference in the conversion behavior of phenol methylation, in the presence of either the carbene or 1,8-diazabicycloundec-7-ene (DBU) catalyst, was rationalized on the basis of mechanistic investigations. The primary mode of action for the N-heterocyclic carbene is nucleophilic catalysis. Activation of the dialkyl carbonate electrophile results in concomitant evolution of an organo-soluble alkoxide, which deprotonates the phenolic starting material. In contrast, DBU is initially protonated by the phenol and thus consumed. Subsequent regeneration and participation in nucleophilic catalysis only becomes significant after some phenolate alkylation occurs. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Explicit role of dynamical and nondynamical electron correlation on singlet-triplet splitting in carbenes

    International Nuclear Information System (INIS)

    Seal, Prasenjit; Chakrabarti, Swapan

    2007-01-01

    Density functional theoretical studies have been performed on carbene systems to determine the singlet-triplet splitting and also to explore the role of electron correlation. Using an approximate method of separation of dynamical and nondynamical correlation, it is found that dynamical and nondynamical electron correlation stabilizes the singlet state relative to the triplet for halo carbenes in both BLYP and B3LYP methods. Calculations performed on higher homologues of methylene suggest that beyond CH(CH 3 ), both the electron correlations have leveling effect in stabilizing the singlet state relative to the triplet. It has also been observed while dynamical electron correlation fails to provide any substantial degree of stabilization to the singlet states of higher homologues of methylene in B3LYP method, an opposite trend is observed for nondynamical counterpart. Among the larger systems studied (9-triptycyl)(α-naphthyl)-carbene has the highest stability of the triplet state whereas bis-imidazol-2-ylidenes has the most stable singlet state. Interestingly, the values of the dynamical electron correlation for each state of each system studied are different for the two methods used. The reason behind this apparent discrepancy lies in the fact that the coefficients of the LYP part in B3LYP and BLYP functionals are different

  10. Engineering of RuMb: Toward a Green Catalyst for Carbene Insertion Reactions.

    Science.gov (United States)

    Wolf, Matthew W; Vargas, David A; Lehnert, Nicolai

    2017-05-15

    The small, stable heme protein myoglobin (Mb) was modified through cofactor substitution and mutagenesis to develop a new catalyst for carbene transfer reactions. The native heme was removed from wild-type Mb and several Mb His64 mutants (H64D, H64A, H64V), and the resulting apoproteins were reconstituted with ruthenium mesoporphyrin IX (RuMpIX). The reconstituted proteins (RuMb) were characterized by UV-vis and circular dichroism spectroscopy and were used as catalysts for the N-H insertion of aniline derivatives and the cyclopropanation of styrene derivatives. The best catalysts for each reaction were able to achieve turnover numbers (TON) up to 520 for the N-H insertion of aniline, and 350 TON for the cyclopropanation of vinyl anisole. Our results show that RuMb is an effective catalyst for N-H insertion, with the potential to further increase the activity and stereoselectivity of the catalyst in future studies. Compared to native Mb ("FeMb"), RuMb is a more active catalyst for carbene transfer reactions, which leads to both heme and protein modification and degradation and, hence, to an overall much-reduced lifetime of the catalyst. This leads to lower TONs for RuMb compared to the iron-containing analogues. Strategies to overcome this limitation are discussed. Finally, comparison is also made to FeH64DMb and FeH64AMb, which have not been previously investigated for carbene transfer reactions.

  11. Reduction of the Work Function of Gold by N-Heterocyclic Carbenes

    KAUST Repository

    Kim, Hye Kyung; Hyla, Alexander; Winget, Paul; Li, Hong; Wyss, Chelsea M.; Jordan, Abraham J.; Larrain, Felipe A.; Sadighi, Joseph P.; Fuentes-Hernandez, Canek; Kippelen, Bernard; Bredas, Jean-Luc; Barlow, Stephen; Marder, Seth R.

    2017-01-01

    N-Heterocyclic carbenes (NHCs) bind strongly to gold and other metals. This work experimentally probes the effect of NHCs on the work function (WF) of gold for the first time, theoretically analyzes the origin of this effect, and examines the effectiveness of NHC-modified gold as an electron-injecting electrode. UV photoelectron spectroscopy shows the WF of planar gold is reduced by nearly 2 eV to values of 3.3–3.5 eV. This effect is seen for NHCs with various heterocyclic cores, and with either small or large N,N′-substituents. DFT calculations indicate the WF reduction results from both the interface dipole formed between the NHC and the gold and from the NHC molecular dipole. For N,N′-diisopropyl-NHCs, an important contributor to the former is charge transfer associated with coordination of the carbene carbon atom to gold. In contrast, the carbene carbon of N,N′-2,6-diisopropylphenyl-NHCs is not covalently bound to gold, resulting in a lower interface dipole; however, a larger molecular dipole partially compensates for this. Single-layer C60 diodes with NHC-modified gold as the bottom electrode demonstrate high rectification ratios and show that these electrodes can act as effective electron-injecting contacts, suggesting they may be useful for a variety of materials applications.

  12. Removal of Hexavalent Chromium from Aqueous Solutions using ...

    African Journals Online (AJOL)

    The hexavalent chromium exists in aquatic media as water soluble complex anions and persist. These are concentrated in industrial waste water especially from the tannery industries and release of effluents from industries adversely affects the environment. The removal of heavy metals from aqueous solutions is carried ...

  13. Antibacterial and DNA cleavage activity of carbonyl functionalized N-heterocyclic carbene-silver(I) and selenium compounds

    Science.gov (United States)

    Haque, Rosenani A.; Iqbal, Muhammad Adnan; Mohamad, Faisal; Razali, Mohd R.

    2018-03-01

    The article describes syntheses and characterizations of carbonyl functionalized benzimidazolium salts, I-IV. While salts I-III are unstable at room temperature, salt IV remained stable and was further utilised to form N-heterocyclic carbene (NHC) compounds of silver(I), V and VI, and selenium compound, VII respectively. Compounds IV-VII were tested for their antibacterial potential against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus). Salt IV shows a very low inhibition potential (minimum inhibitory concentration, MIC 500 μg/mL) compared to the respective silver(I)-NHC, V and VI (MIC 31.25 μg/mL against both, E. coli and S. aureus) and selenium compound, VII (MIC 125 μg/mL against E. coli and 62.50 μg/mL against S. aureus). In DNA cleavage abilities, all the test compounds cleave DNA in which the VII cleaves the DNA at the faster rate. Meanwhile, the silver(I)-NHC complexes V and VI act at the same mode and pattern of DNA cleavage while VII is similar to IV.

  14. Olefin Metathesis with Ru-Based Catalysts Exchanging the Typical N-Heterocyclic Carbenes by a Phosphine–Phosphonium Ylide

    Directory of Open Access Journals (Sweden)

    Laia Arnedo

    2017-03-01

    Full Text Available Density functional theory (DFT calculations have been used to describe the first turnover of an olefin metathesis reaction calling for a new in silico family of homogenous Ru-based catalysts bearing a phosphine–phosphonium ylide ligand, with ethylene as a substrate. Equal to conventional Ru-based catalysts bearing an N-heterocyclic carbene (NHC ligand, the activation of these congeners occurs through a dissociative mechanism, with a more exothermic first phosphine dissociation step. In spite of a stronger electron-donating ability of a phosphonium ylide C-ligand with respect to a diaminocarbene analogue, upper energy barriers were calculated to be on average ca. 5 kcal/mol higher than those of Ru–NHC standards. Overall, the study also highlights advantages of bidentate ligands over classical monodentate NHC and phosphine ligands, with a particular preference for the cis attack of the olefin. The new generation of catalysts is constituted by cationic complexes potentially soluble in water, to be compared with the typical neutral Ru–NHC ones.

  15. Supporting Information Palladium Complexes of a New Type of N ...

    Indian Academy of Sciences (India)

    Prasenjit Ghosh

    Palladium Complexes of a New Type of N-heterocyclic Carbene. Ligand Derived From a Tricyclic Triazolooxazine Framework. Manoj Kumar Gangwar, Alok Ch. Kalita and Prasenjit Ghosh*. Department of Chemistry,. Indian Institute of Technology Bombay, ... 2. Figure S1. 1. H NMR spectrum of the compound 1a in CDCl3.

  16. Chromium isotope variations

    DEFF Research Database (Denmark)

    D'Arcy, Joan Mary

    the δ53Cr value of continental runoff into the ocean. The major findings were that river water is characterised by heavy δ53Cr values (+0.1‰ to +1.6‰), while soils are characterised by light δ53Cr values (-0.3‰), relative to the catchment bedrock (-0.17‰ to -0.21‰), indicating that Cr isotopes......, and the quantification the Cr isotope composition of major Cr fluxes into and out of ocean. This thesis adds to the current knowledge of the Cr isotope system and is divided into two studies. The focus of the first study was to determine what processes control the Cr isotopic compositionof river water and to quantify......Chromium (Cr) stable isotopes are a useful tracer of changes in redox conditions because changes in its oxidation state are accompanied by an isotopic fractionation. For this reason the Cr isotope system is being developed as a potential tool for paleo-redox reconstruction. Dissolved Cr in seawater...

  17. Trivalent chromium removal from aqueous solutions by a sol–gel synthesized silica adsorbent functionalized with sulphonic acid groups

    Energy Technology Data Exchange (ETDEWEB)

    Gomez-Gonzalez, Sergio Efrain [Departamento de Ingeniería Química, Universidad de Guadalajara, Blvd. Marcelino García Barragán # 1421, esq. Calzada Olímpica, C.P. 44430 Guadalajara, Jalisco (Mexico); Carbajal-Arizaga, Gregorio Guadalupe [Departamento de Química, CUCEI, Universidad de Guadalajara, Blvd. Marcelino García Barragán # 1421, esq. Calzada Olímpica, C.P. 44430 Guadalajara, Jalisco (Mexico); Manriquez-Gonzalez, Ricardo [Departamento de Madera, Celulosa y Papel, CUCEI, Universidad de Guadalajara, Km 15.5, carretera Guadalajara-Nogales, Las Agujas, C.P. 45020 Zapopan, Jalisco (Mexico); De la Cruz-Hernandez, Wencel [Centro de Nanociencias y Nanotecnología, Universidad Nacional Autónoma de México, Km 107 carretera Tijuana-Ensenada, C.P. 22830 Ensenada, Baja California (Mexico); Gomez-Salazar, Sergio, E-mail: sergio.gomez@cucei.udg.mx [Departamento de Ingeniería Química, Universidad de Guadalajara, Blvd. Marcelino García Barragán # 1421, esq. Calzada Olímpica, C.P. 44430 Guadalajara, Jalisco (Mexico)

    2014-11-15

    Highlights: • Corpuscular sulphonic acid-functionalized silica holds improved uptake of chromium. • Mesopores on adsorbent facilitate (CH{sub 3}COO){sub 2}Cr{sup +} ion uptake on sulphonate sites. • Formation of chromium acetate sulphonate complex proposed from XPS results. • Fixed bed chromium uptake results suggest potential industrial use. - Abstract: A high capacity hybrid silica adsorbent was synthesized via sol–gel processing with sulphonic acid groups as trivalent chromium complex ions chelators from aqueous solutions. The synthesis included co-condensation of tetraethoxysilane (TEOS) with 3-(mercaptopropyl)trimethoxysilane (MPS), and oxidation of thiol to sulphonic acid groups. Chromium uptake kinetic, batch and fixed-bed experiments were performed to assess the removal of this metal from aqueous solutions. {sup 13}C, {sup 29}Si CPMAS NMR, FTIR, XPS were used to characterize the adsorbent structure and the nature of chromium complexes on the adsorbent surface. Chromium maximum uptake was obtained at pH 3 (72.8 mg/g). Elemental analysis results showed ligand density of 1.48 mmol sulphonic groups/g. About 407 mL of Cr(III) solution (311 mg/L) were treated to breakthrough point reaching ≤0.06 mg/L at the effluent. These results comply with USEPA regulation for chromium concentration in drinking water (≤0.1 mg/L). The adsorbent shows potential to be used in chromium separations to the industrial level.

  18. Trivalent chromium removal from aqueous solutions by a sol–gel synthesized silica adsorbent functionalized with sulphonic acid groups

    International Nuclear Information System (INIS)

    Gomez-Gonzalez, Sergio Efrain; Carbajal-Arizaga, Gregorio Guadalupe; Manriquez-Gonzalez, Ricardo; De la Cruz-Hernandez, Wencel; Gomez-Salazar, Sergio

    2014-01-01

    Highlights: • Corpuscular sulphonic acid-functionalized silica holds improved uptake of chromium. • Mesopores on adsorbent facilitate (CH 3 COO) 2 Cr + ion uptake on sulphonate sites. • Formation of chromium acetate sulphonate complex proposed from XPS results. • Fixed bed chromium uptake results suggest potential industrial use. - Abstract: A high capacity hybrid silica adsorbent was synthesized via sol–gel processing with sulphonic acid groups as trivalent chromium complex ions chelators from aqueous solutions. The synthesis included co-condensation of tetraethoxysilane (TEOS) with 3-(mercaptopropyl)trimethoxysilane (MPS), and oxidation of thiol to sulphonic acid groups. Chromium uptake kinetic, batch and fixed-bed experiments were performed to assess the removal of this metal from aqueous solutions. 13 C, 29 Si CPMAS NMR, FTIR, XPS were used to characterize the adsorbent structure and the nature of chromium complexes on the adsorbent surface. Chromium maximum uptake was obtained at pH 3 (72.8 mg/g). Elemental analysis results showed ligand density of 1.48 mmol sulphonic groups/g. About 407 mL of Cr(III) solution (311 mg/L) were treated to breakthrough point reaching ≤0.06 mg/L at the effluent. These results comply with USEPA regulation for chromium concentration in drinking water (≤0.1 mg/L). The adsorbent shows potential to be used in chromium separations to the industrial level

  19. Characteristics of oxidation of low-alloyed chromium in nitrogen tetroxide

    International Nuclear Information System (INIS)

    Kamenev, A.Ya.; Goncharova, N.V.; Kopets, Z.V.; Tedushin, E.E.

    1985-01-01

    The effect of N 2 O 4 on corrosion properties of chromium-based alloys is studied. The method of structural materials analysis is described using as an example chromium-based alloys in the flow of chemically active N 2 O 4 at high temperatures. The method has been used to study corrosive behaviour of chromium at temperatures 923, 1073 and 1273 K. The time of exposure amounts up to 140 hours. The wave-like time dependence of mass velocity variation has been observed for all chromium samples under test. The time of the alloy exposure to N 2 O 4 medium and the nature of the alloying affect this dependence. The given metallograhic studies of chromium alloys show complex structure of the surface layer

  20. Synthesis of a Benzodiazepine-derived Rhodium NHC Complex by C-H Bond Activation

    Energy Technology Data Exchange (ETDEWEB)

    Bergman, Roberg G.; Gribble, Jr., Michael W.; Ellman, Jonathan A.

    2008-01-30

    The synthesis and characterization of a Rh(I)-NHC complex generated by C-H activation of 1,4-benzodiazepine heterocycle are reported. This complex constitutes a rare example of a carbene tautomer of a 1,4-benzodiazepine aldimine stabilized by transition metal coordination and demonstrates the ability of the catalytically relevant RhCl(PCy{sub 3}){sub 2} fragment to induce NHC-forming tautomerization of heterocycles possessing a single carbene-stabilizing heteroatom. Implications for the synthesis of benzodiazepines and related pharmacophores via C-H functionalization are discussed.

  1. Specification for corrosion-resisting chromium and chromium-nickel steel covered welding electrodes

    International Nuclear Information System (INIS)

    Anon.

    1983-01-01

    This specification prescribes requirements for covered corrosion-resisting chromium and chromium-nickel steel electrodes. These electrodes normally are used for shielded metal arc welding, and include those alloy steels designated as corrosion or heat-resisting chromium-nickel steels in which chromium exceeds 4.0 percent and nickel does not exceed 50.0 percent

  2. Chromium Uptake Efficiency of Spinacea olaracea from ...

    African Journals Online (AJOL)

    The aim of the study was to evaluate the uptake of chromium by Spinacea olaracea and its accumulation in roots and shoots of plants grown in pots at various concentrations of chromium (30, 60, 90,120,150 mg/l). The results revealed that the levels of chromium accumulation in roots and shoots were higher at minimum ...

  3. On texture formation of chromium electrodeposits

    DEFF Research Database (Denmark)

    Nielsen, Christian Bergenstof; Leisner, Peter; Horsewell, Andy

    1998-01-01

    The microstructure, texture and hardness of electrodeposited hard, direct current (DC) chromium and pulsed reversed chromium has been investigated. These investigations suggest that the growth and texture of hard chromium is controlled by inhibition processes and reactions. Further, it has been...

  4. N-Heterocyclic Carbene-Catalysed Diastereoselective Vinylogous Michael Addition Reaction of gamma-Substituted deconjugated Butenolides

    KAUST Repository

    Guo, Hao; Xing, Fen; Du, Guang-Fen; Huang, Kuo-Wei; Dai, Bin; He, Lin

    2015-01-01

    An efficient N-heterocyclic carbene (NHC)-catalysed vinylogous Michael addition of deconjugated butenolides was developed. In the presence of 5 mol% of the NHC catalyst, both γ-alkyl and aryl-substituted deconjugated butenolides undergo vinylogous Michael addition with various α, β-unsaturated ketones, esters, or nitriles to afford γ,γ-disubstituted butenolides containing adjacent quaternary and tertiary carbon centers in good to excellent yields with excellent diastereoselectivities. In this process, the free carbene is assumed to act as a strong Brønsted base to promote the conjugate addition.

  5. N-Heterocyclic Carbene-Catalysed Diastereoselective Vinylogous Michael Addition Reaction of gamma-Substituted deconjugated Butenolides

    KAUST Repository

    Guo, Hao

    2015-11-16

    An efficient N-heterocyclic carbene (NHC)-catalysed vinylogous Michael addition of deconjugated butenolides was developed. In the presence of 5 mol% of the NHC catalyst, both γ-alkyl and aryl-substituted deconjugated butenolides undergo vinylogous Michael addition with various α, β-unsaturated ketones, esters, or nitriles to afford γ,γ-disubstituted butenolides containing adjacent quaternary and tertiary carbon centers in good to excellent yields with excellent diastereoselectivities. In this process, the free carbene is assumed to act as a strong Brønsted base to promote the conjugate addition.

  6. Advances In Hexavalent Chromium Removal At Hanford

    International Nuclear Information System (INIS)

    Neshem, D.O.; Riddelle, J.

    2012-01-01

    At the Hanford Site, chromium was used as a corrosion inhibitor in the reactor cooling water and was introduced into the groundwater as a result of planned and unplanned discharges from reactors during plutonium production since 1944. Beginning in 1995, groundwater treatment methods were evaluated leading to the use of pump and treat facilities with ion exchange using Dowex 21 K, a regenerable strong base anion exchange resin. This required regeneration of the resin, which is currently performed offsite. Resin was installed in a 4 vessel train, with resin removal required from the lead vessel approximately once a month. In 2007, there were 8 trains (32 vessels) in operation. In 2008, DOE recognized that regulatory agreements would require significant expansion in the groundwater chromium treatment capacity. Previous experience from one of the DOE project managers led to identification of a possible alternative resin, and the contractor was requested to evaluate alternative resins for both cost and programmatic risk reductions. Testing was performed onsite in 2009 and 2010, using a variety of potential resins in two separate facilities with groundwater from specific remediation sites to demonstrate resin performance in the specific groundwater chemistry at each site. The testing demonstrated that a weak base anion single-use resin, ResinTech SIR-700, was effective at removing chromium, had a significantly higher capacity, could be disposed of efficiently on site, and would eliminate the complexities and programmatic risks from sampling, packaging, transportation and return of resin for regeneration. This resin was installed in Hanford's newest groundwater treatment facility, called 100-DX, which began operations in November, 2010, and used in a sister facility, 100-HX, which started up in September of 2011. This increased chromium treatment capacity to 25 trains (100 vessels). The resin is also being tested in existing facilities that utilize Dowex 21 K for

  7. The electrochemistry of chromium, chromium-boron and chromium-phosphorus alloys

    International Nuclear Information System (INIS)

    Moffat, T.P.; Ruf, R.R.; Latanision, R.M.

    1987-01-01

    It is fairly well established that chromium-metalloid interactions represent the key to understanding the remarkable corrosion behavior of TM-Cr-M glasses; (Fe, Ni, Co,...)-Cr-(P, Si, C, S). The character and kinetics of passive film growth on the glasses are being studied ni order to assess the role of the film former, chromium, and the metalloids in the passivation process. A series of thin film microcrystalline chromium, Cr-B and Cr-P binary alloys have been fabricated by physical vapor deposition techniques. Vacuum melted conventionally processed chromium has also been studied. Examination of these materials in lM H/sub 2/SO/sub 4/ and lM HCl by voltammetry, potentiostatic and impedance techniques yields the following conclusion: 1. Pure chromium with a grain size varying from < 400 A to 0.5 mm exhibits no well defined differences in electrochemical behavior in lM H/sub 2/SO/sub 4/. 2. The tremendous corrosion resistance of Cr-B alloys has been confirmed. 3. The beneficial effects observed for boron alloyed with chromium may be considered surprising in view of the neutral/negative influence of alloying boron with iron, i.e. Fe/sub 80/B/sub 20/. 4. The interaction of the electrochemistry of the metalloid constituent with that of the transition base element determines the corrosion behavior. 5. Preliminary work with Cr-P alloys indicates that certain compositions exhibit promising properties - certain films were found to be intact after two days of immersion in concentrated HCl. Further work is in progress

  8. Quantum and Statistical Mechanics Applied to Singlet Carbenes, Pericyclic Reactions, and Condensed Phase Phenomena

    Science.gov (United States)

    Evanseck, Jeffrey Donald

    The completed research covers a broad range of theoretical applications in organic chemistry. It is divided into three chapters which covers the chemistry of singlet carbenes (Chapter 1), substituent effects in pericyclic rearrangements (Chapter 2), and the effects of solvent on the reactivity of organic reactions (Chapter 3). The selectivity between 1,2- and 1,4-intramolecular additions to restricted diene systems has been investigated. A decrease in activation energy for the intramolecular cycloaddition is noted for systems which approach the idealized geometry found with intermolecular addition of carbenes to olefins. Direct substitution at the carbene site dramatically effects the predicted activation barriers for 1,2-hydrogen shifts. An excellent correlation between the activation energy and a substituents sigma_sp {rm R}{rm o} parameters has been demonstrated. The long standing problem of orbital alignment influences on the selectivity of 1,2-hydrogen arrangements shows significant geometric distortions, yet has little influence on the rates of singlet alkylcarbene rearrangements. The exo-selectivities observed for 1,2-shifts in rigid systems are explained by torsional and steric interactions which develop in the transition structures. Substituent effects on pericyclic reactions have been computed for several conrotatory and disrotatory electrocyclizations. The six-electron disrotatory electrocyclization of 1-substituted hexatrienes displays a strong electronic component in determining stereoselectivity, despite incredible steric interference. The eight-electron conrotatory electrocyclization transition structure of 1-substituted octatetraene has an unusual helical transition structure which does not differentiate between substituent position. The effects of solvents on the acidity differences between E and Z esters has supplemented earlier ab initio quantum mechanical results on the enhanced acidity of Meldrum's acid. Monte Carlo simulations predict a

  9. Theoretical studies of mechanisms of cycloaddition reaction between difluoromethylene carbene and acetone

    Science.gov (United States)

    Lu, Xiu Hui; Yu, Hai Bin; Wu, Wei Rong; Xu, Yue Hua

    Mechanisms of the cycloaddition reaction between singlet difluoromethylene carbene and acetone have been investigated with the second-order Møller-Plesset (MP2)/6-31G* method, including geometry optimization and vibrational analysis. Energies for the involved stationary points on the potential energy surface (PES) are corrected by zero-point energy (ZPE) and CCSD(T)/6-31G* single-point calculations. From the PES obtained with the CCSD(T)//MP2/6-31G* method for the cycloaddition reaction between singlet difluoromethylene carbene and acetone, it can be predicted that path B of reactions 2 and 3 should be two competitive leading channels of the cycloaddition reaction between difluoromethylene carbene and acetone. The former consists of two steps: (i) the two reactants first form a four-membered ring intermediate, INT2, which is a barrier-free exothermic reaction of 97.8 kJ/mol; (ii) the intermediate INT2 isomerizes to a four-membered product P2b via a transition state TS2b with an energy barrier of 24.9 kJ/mol, which results from the methyl group transfer. The latter proceeds in three steps: (i) the two reactants first form an intermediate, INT1c, through a barrier-free exothermic reaction of 199.4 kJ/mol; (ii) the intermediate INT1c further reacts with acetone to form a polycyclic intermediate, INT3, which is also a barrier-free exothermic reaction of 27.4 kJ/mol; and (iii) INT3 isomerizes to a polycyclic product P3 via a transition state TS3 with an energy barrier of 25.8 kJ/mol.

  10. Enantioselective N-Heterocyclic Carbene Catalysis via the Dienyl Acyl Azolium.

    Science.gov (United States)

    Gillard, Rachel M; Fernando, Jared E M; Lupton, David W

    2018-04-16

    Herein we report the enantioselective N-heterocyclic carbene catalyzed (4+2) annulation of the dienyl acyl azolium with enolates. The reaction exploits readily accessible acyl fluorides and TMS enol ethers to give a range of highly enantio- and diastereo-enriched cyclohexenes (most >97:3 er and >20:1 dr). The reaction was found to require high nucleophilicity NHC catalysts with mechanistic studies supporting a stepwise 1,6-addition/β-lactonization. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Aminomethylation of enals through carbene and acid cooperative catalysis: concise access to β(2)-amino acids.

    Science.gov (United States)

    Xu, Jianfeng; Chen, Xingkuan; Wang, Ming; Zheng, Pengcheng; Song, Bao-An; Chi, Yonggui Robin

    2015-04-20

    A convergent, organocatalytic asymmetric aminomethylation of α,β-unsaturated aldehydes by N-heterocyclic carbene (NHC) and (in situ generated) Brønsted acid cooperative catalysis is disclosed. The catalytically generated conjugated acid from the base plays dual roles in promoting the formation of azolium enolate intermediate, formaldehyde-derived iminium ion (as an electrophilic reactant), and methanol (as a nucleophilic reactant). This redox-neutral strategy is suitable for the scalable synthesis of enantiomerically enriched β(2) -amino acids bearing various substituents. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Chromium Chemistry in the Subsurface

    Science.gov (United States)

    Chromium (VI) (Cr) is carcinogenic and a threat to human and ecological health. There are adequate and acceptable methods to characterize and assess Cr contaminated sites. Cr chemistry in the environment is well understood. There are documented methods to address Cr contaminat...

  13. Iron-nickel-chromium alloys

    International Nuclear Information System (INIS)

    Karenko, M.K.

    1981-01-01

    A specification is given for iron-nickel-chromium age-hardenable alloys suitable for use in fast breeder reactor ducts and cladding, which utilize the gamma-double prime strengthening phase and are characterized in having a delta or eta phase distributed at or near grain boundaries. A range of compositions is given. (author)

  14. Treatment of chromium contaminated soil using bioremediation

    Science.gov (United States)

    Purwanti, Ipung Fitri; Putri, Tesya Paramita; Kurniawan, Setyo Budi

    2017-11-01

    Chromium contamination in soil occurs due to the disposal of chromium industrial wastewater or sludge that excess the quality standard. Chromium concentration in soil is ranged between 1 to 300 mg/kg while the maximum health standard is 2.5 mg/kg. Bioremediation is one of technology that could be used for remediating heavy metal contamination in soil. Bacteria have an ability to remove heavy metal from soil. One bacteria species that capable to remove chromium from soil is Bacillus subtilis. The aim of this research was to know the chromium removal percentage in contaminated soil by Bacillus subtilis. Artificial chromium contaminated soil was used by mixing 425gram sand and chromium trichloride solution. Concentration of chromium added into the spiked soil were 50, 75, and 100 mg/L. During 14 days, pH, soil temperature and soil moisture were tested. Initial and final number of bacterial colony and chromium concentration analysed. The result showed that the highest percentage of chromium removal was 11% at a chromium concentration of 75 mg/L

  15. Unusual NHC-Iridium(I) Complexes and Their Use in the Intramolecular Hydroamination of Unactivated Aminoalkenes

    KAUST Repository

    Sipos, Gellé rt; Ou, Arnold; Skelton, Brian W.; Falivene, Laura; Cavallo, Luigi; Dorta, Reto

    2016-01-01

    N-heterocyclic carbene (NHC) ligands with naphthyl side chains were employed for the synthesis of unsaturated, yet isolable [(NHC)Ir(cod)]+ (cod=1,5-cyclooctadiene) complexes. These compounds are stabilised by an interaction of the aromatic wingtip that leads to a sideways tilt of the NHC-Ir bond. Detailed studies show how the tilting of such N-heterocyclic carbenes affects the electronic shielding properties of the carbene carbon atom and how this is reflected by significant upfield shifts in the 13CNMR signals. When employed in the intramolecular hydroamination, these [(NHC)Ir(cod)]+ species show very high catalytic activity under mild reaction conditions. An enantiopure version of the catalyst system produces pyrrolidines with excellent enantioselectivities. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Unusual NHC-Iridium(I) Complexes and Their Use in the Intramolecular Hydroamination of Unactivated Aminoalkenes

    KAUST Repository

    Sipos, Gellért

    2016-04-10

    N-heterocyclic carbene (NHC) ligands with naphthyl side chains were employed for the synthesis of unsaturated, yet isolable [(NHC)Ir(cod)]+ (cod=1,5-cyclooctadiene) complexes. These compounds are stabilised by an interaction of the aromatic wingtip that leads to a sideways tilt of the NHC-Ir bond. Detailed studies show how the tilting of such N-heterocyclic carbenes affects the electronic shielding properties of the carbene carbon atom and how this is reflected by significant upfield shifts in the 13CNMR signals. When employed in the intramolecular hydroamination, these [(NHC)Ir(cod)]+ species show very high catalytic activity under mild reaction conditions. An enantiopure version of the catalyst system produces pyrrolidines with excellent enantioselectivities. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Determination of chromium combined with DNA, RNA and protein in chromium-rich brewer's yeast

    International Nuclear Information System (INIS)

    Ding Wenjun; Qian Qinfang; Hou Xiaolin; Feng Weiyue; Chai Zhifang

    2000-01-01

    The contents of chromium in the DNA, RNA and protein fractions separated from chromium-rich and normal brewer's yeast were determined with the neutron activation analysis in order to study the combination of Cr with DNA, RNA and protein in chromium-rich brewer's yeast. The results showed that the extracting rats and concentrations of DNA, RNA and protein had no significant difference in two types of yeast, but the chromium contents of DNA, RNA and protein in the chromium-rich yeast were significantly higher than those in the normal. In addition, the content of chromium in DNA was much higher than that in RNA and protein, which indicated that the inorganic chromium compounds entered into the yeast cell, during the yeast cultivation in the culture medium containing chromium were converted into organic chromium compounds combined with DNA, RNA and protein

  18. Reductive coupling of carbon monoxide in a rhenium carbonyl complex with pendant Lewis acids.

    Science.gov (United States)

    Miller, Alexander J M; Labinger, Jay A; Bercaw, John E

    2008-09-10

    Phosphinoborane ligands impart unique reactivity to a rhenium carbonyl cation relative to simple phosphine complexes. Addition of either triethylborohydride or a platinum hydride (that can be formed from H2) forms a rhenium boroxycarbene. This carbene, which crystallizes as a dimer, disproportionates over a period of days to afford the starting cation and a structurally unprecedented boroxy(boroxymethyl)carbene, in which a new C-C bond has been formed between two reduced CO ligands. This product of C-C bond formation can be independently synthesized by addition of 2 equiv of hydride to the rhenium carbonyl cation.

  19. Complexes carbéniques nucléophiles de l'uranium

    OpenAIRE

    Tourneux , Jean-Christophe

    2012-01-01

    The only stable f-metal carbene complexes (excluding NHC) metals f present R2C(2-) groups having one or two phosphorus atoms in the central carbon in alpha position. The objective of this work was to develop the chemistry of carbenes for uranium (metal 5f) with the dianion C{Ph2P(=S)}2(2-) (SCS(2-)) to extend the organometallic chemistry of this element in its various oxidation states (+3-6), and to reveal the influence of the 5f orbitals on the nature and reactivity of the double bond C=U.We...

  20. Potentiometric determination of the tungsten content of tantalum-tungsten alloys with chromium II

    International Nuclear Information System (INIS)

    Gavra, Z.; Ronen, S.; Levin, R.

    1977-05-01

    A method was developed for the potentiometric determination of the tungsten content of tantalum-tungsten alloys of different compositions. These were dissolved under conditions that enabled the tungsten content to be determined with chromium (II). Phosphoric acid was selected as a suitable complexing agent for the prevention of the precipitation of tungsten and tantalum compounds. The use of chromium (II) required an oxygen-tight system and therefore the work was carried out in suitable vessels for storage and tritation

  1. Synthesis, characterisation and modelling of a ferromagnetically coupled chromium(III) Dimer

    DEFF Research Database (Denmark)

    Morsing, Thorbjørn Juul; Weihe, Høgni; Bendix, Jesper

    2014-01-01

    A rare example of a ferromagnetically coupled dinuclear chromium(III) complex, the di-μ-hydroxobis[tetrakis(isothiocyanato)chromate(III)] anion, is reported. This complex has been synthesised from the oxo-bridged acetonitrile complex [(CH3CN)5CrOCr(NCCH3)5](BF4)4 and isolated as the solvated...

  2. Chromium in aqueous nitrate plutonium process streams: Corrosion of 316 stainless steel and chromium speciation

    International Nuclear Information System (INIS)

    Smith, W.H.; Purdy, G.

    1994-01-01

    According to the measurements made in this study, the only situation in which chromium (+6) could exist in a plutonium process solution is one in which a feed containing chromium is dissolved in a glass pot dissolver in high nitric acid concentration and at high temperature. But when the resulting feed is prepared for ion exchange, the chemical treatment reduces chromium to the +3 state. Any solution being processed through the evaporator will only contain chromium in the +3 state and any chromium salts remaining in the evaporator bottoms will be chromium +3 salts

  3. N-Heterocyclic-Carbene-Catalysed Diastereoselective Vinylogous Mukaiyama/Michael Reaction of 2-(Trimethylsilyloxy)furan and Enones

    KAUST Repository

    Wang, Ying; Du, Guang Fen; Xing, Fen; Huang, Kuo-Wei; Dai, Bin; He, Lin

    2015-01-01

    N-heterocyclic carbenes have been utilised as highly efficient nucleophilic organocatalysts to mediate vinylogous Mukaiyama/Michael reactions of 2-(trimethylsilyloxy)furan with enones to afford γ-substituted butenolides in 44-99% yield with 3:1-32:1 diastereoselectivity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Optimized Syntheses of Cyclopentadienyl Nickel Chloride Compounds Containing "N"-Heterocyclic Carbene Ligands for Short Laboratory Periods

    Science.gov (United States)

    Cooke, Jason; Lightbody, Owen C.

    2011-01-01

    Experiments are described for the preparation of imidazolium chloride precursors to "N"-heterocyclic carbenes and their cyclopentadienyl nickel chloride derivatives. The syntheses have been optimized for second- and third-year undergraduate laboratories that have a maximum programmed length of three hours per week. The experiments are flexible and…

  5. Auranofin and N-heterocyclic carbene gold-analogs are potent inhibitors of the bacteria Helicobacter pylori.

    Science.gov (United States)

    Owings, Joshua P; McNair, Nina N; Mui, Yiu Fung; Gustafsson, Tomas N; Holmgren, Arne; Contel, Maria; Goldberg, Joanna B; Mead, Jan R

    2016-07-01

    Auranofin is an FDA-approved gold-containing compound used for the treatment of rheumatoid arthritis. Recent reports of antimicrobial activity against protozoa and bacteria indicate that auranofin targets the reductive enzyme thioredoxin reductase (TrxR). We evaluated auranofin as well as five auranofin analogs containing N-heterocyclic carbenes (instead of the triethylphosphane present in auranofin) and five gold-carbene controls for their ability to inhibit or kill Helicobacter pylori in vitro Auranofin completely inhibited bacterial growth at 1.2 μM. Purified H. pylori TrxR was inhibited by auranofin in a cell-free assay (IC50 ∼88 nM). The most active gold(I)-N-heterocyclic carbene compounds exhibited MICs comparable to auranofin against H. pylori (2 μM), while also exhibiting lower toxicities for human embryonic kidney cells (HEK-293T cells). Median toxic concentrations (TC50) were 13-20-fold higher compared to auranofin indicating that they were less cytotoxic. The N-heterocyclic carbene analogs maybe well tolerated, but further evaluation is needed in vivo Finally, auranofin was synergistic with the antibiotic amoxicillin, suggesting that targeting both the reductive enzyme TrxR and cell wall synthesis may be effective against H. pylori infections. © FEMS 2016. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

  6. N-Heterocyclic-Carbene-Catalysed Diastereoselective Vinylogous Mukaiyama/Michael Reaction of 2-(Trimethylsilyloxy)furan and Enones

    KAUST Repository

    Wang, Ying

    2015-10-15

    N-heterocyclic carbenes have been utilised as highly efficient nucleophilic organocatalysts to mediate vinylogous Mukaiyama/Michael reactions of 2-(trimethylsilyloxy)furan with enones to afford γ-substituted butenolides in 44-99% yield with 3:1-32:1 diastereoselectivity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Responses of endogenous proline in rice seedlings under chromium exposure

    Directory of Open Access Journals (Sweden)

    X.Z. Yu

    2016-12-01

    Full Text Available Hydroponic experiments were performed to exam the dynamic change of endogenous proline in rice seedlings exposed to potassium chromate chromium (VI or chromium nitrate chromium (III. Although accumulation of both chromium species in rice seedlings was obvious, more chromium was detected in plant tissues of rice seedlings exposed to chromium (III than those in chromium (VI, majority being in roots rather than shoots. Results also showed that the accumulation capacity of chromium by rice seedlings was positively correlated to chromium concentrations supplied in both chromium variants and the accumulation curve depicted an exponential trend in both chromium treatments over the entire period of exposure. Proline assays showed that both chromium variants induced the change of endogenous proline in shoots and roots of rice seedlings. Chromium (VI of 12.8 mg/L increased proline content significantly (p

  8. Chromium base high performance materials: Where and how do they come from?

    Science.gov (United States)

    Choi, In-Kap

    1996-08-01

    The origin of chromium base performance materials (CBPM) is described. CBPM may include (1) trivalent chromium chemicals such as chromic acetate, chromic chloride, chromic bromide, chromic fluoride, chromic iodide, chromic phosphate, and chromic sulfate; (2) hexavalent chromium chemicals such as chromic acid, lithium chromate, sodium chromate, sodium dichromate, and potassium dichromate; (3) oxide forms of chromium such as black chrome, chromium dioxide, chromium oxide, and chromium hydroxide; and (4) other chromium compounds such as chromium aluminide, chromium boride, chromium carbide, chromium molybdate, chromium nitride, chromium silicide, chromium tungstate and lanthanum chromite. Extensive reviews of production processes, properties, and applications/end uses of CBPM are made.

  9. Synthesis of chromium containing pigments from chromium galvanic sludges

    International Nuclear Information System (INIS)

    Andreola, F.; Barbieri, L.; Bondioli, F.; Cannio, M.; Ferrari, A.M.; Lancellotti, I.

    2008-01-01

    In this work the screening results of the scientific activity conducted on laboratory scale to valorise chromium(III) contained in the galvanic sludge as chromium precursor for ceramic pigments are reported. The valorisation of this waste as a secondary raw material (SRM) is obtained by achievement of thermal and chemical stable crystal structures able to color ceramic material. Two different pigments pink CaCr 0.04 Sn 0.97 SiO 5 and green Ca 3 Cr 2 (SiO 4 ) 3 were synthesized by solid-state reactions using dried Cr sludge as chromium oxide precursor. The obtained pigments were characterized by X-ray diffraction and SEM analysis. Furthermore the color developed in a suitable ceramic glaze was investigated in comparison with the color developed by the pigments prepared from pure Cr 2 O 3 . The characterization carried out corroborates the thermal and chemical stability of the synthesized pigments and, especially for the Cr-Sn pink pigment, the powders develop an intense color that is very similar to the color developed by the pigments obtained starting from pure Cr 2 O 3

  10. Group 4 Transition-Metal Complexes of an Aniline–Carbene–Phenol Ligand

    KAUST Repository

    Despagnet-Ayoub, Emmanuelle

    2013-05-24

    Attempts to install a tridentate aniline-NHC-phenol (NCO) ligand on titanium and zirconium led instead to complexes resulting from unexpected rearrangement pathways that illustrate common behavior in carbene-early- transition-metal chemistry. © 2013 American Chemical Society.

  11. Effect of chromium on plants

    Energy Technology Data Exchange (ETDEWEB)

    Fuissello, N.; Novo, P.

    1976-01-01

    Chromium as K/sub 2/Cr/sub 2/O/sub 7/ and Cr(NO/sub 3/)/sub 3/, was tested for its toxicity, in Petri dishes, on 10 species of crop plants at 1 - 10 - 100 ppm. The total number of germinated seeds is not affected by Chromium salts up to 100 ppm, but the toxicity, measured as diminution of growth, is evident for all the tested plants, at 100 ppm, both with Cr/sup +3/ and Cr/sup +6/. Cr/sup +6/ at 1 ppm shows a negative effect on growth only for Linum usitatissimum, that could be used in phyto-test for polluted waters. Cr/sup +6/ was revealed more toxic than Cr/sup +3/ for plants, as reported for animals. 14 references, 6 figures, 3 tables.

  12. Simultaneous determination of chromium(III) and chromium(VI) in aqueous solutions by ion chromatography and chemiluminescence detection

    DEFF Research Database (Denmark)

    Gammelgaard, Bente; Jøns, O; Nielsen, B

    1992-01-01

    A method for the simultaneous determination of chromium(iii) and chromium(vi) in a flow system based on chemiluminescence was developed. A Dionex cation-exchange guard column was used to separate chromium(iii) from chromium(vi), and chromium(vi) was reduced by potassium sulfite, whereupon both...

  13. Study of Physical modifications induced by chromium doping of uranium dioxide

    International Nuclear Information System (INIS)

    Fraczkiewicz, M.

    2010-01-01

    Improvement of nuclear fuel performances requires reducing fission gas release. Doping uranium dioxide with chromium is the improvement axis considered in this work. Indeed, chromium fastens crystal growth in UO 2 , and thus enables a significant increase of the grain size. This work aims at the identification of defects produced by chromium addition in UO 2 , and their impact on properties of interest of the material. First, defects existing in doped fuel directly after sintering have been studied. X-ray Absorption Spectroscopy allowed the identification of the environment of solubilised chromium in UO 2 . Chromium atoms are roughly substituting for uranium atoms, but generate a complete reorganisation of neighbouring oxygen atoms, and distortion of uranium sublattice. Characterisation of transport properties (electrical conductivity and oxygen self-diffusion) have shown that because of charge balance, chromium plays a leading role on such properties. A model of point defects in UO 2 has been proposed, showing how complex the involved phenomena are. Observations by Transmission Electron Microscopy of ion-irradiated thin foils have shown that chromium makes the coalescence of irradiation defects easier. This behaviour can be explained by a stabilisation of defect clusters due to precipitation of chromium. Finally, study of thermal diffusion of helium in doped UO 2 , performed by Nuclear Reaction Analysis, has confirmed this interaction between chromium atoms and irradiation defects. Indeed, μ-NRA measures have shown no fast gas diffusion close to grain boundaries, in contrast with standard UO 2 behaviour, which is associated with defects recovery in grain boundaries. (author) [fr

  14. Variation of the Sterical Properties of the N-Heterocyclic Carbene Coligand in Thermally Triggerable Ruthenium-Based Olefin Metathesis Precatalysts/Initiators

    KAUST Repository

    Pump, Eva

    2015-11-09

    A series of ruthenium complexes based on the κ(C,N)-(2-(benzo[h]quinolin-10-yl)methylidene ruthenium dichloride fragment featuring different neutral coligands L (L = 1,3-bis(2,6-diisopropylphenyl)-4,5-dihydroimidazol-2-ylidene (SIPr), 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene (SIMes), 1,3-bis(2,4-dimethylphenyl)-4,5-dihydroimidazol-2-ylidene (SIXyl), and 1,3-bis(2-methylphenyl)-4,5-dihydroimidazol-2-ylidene (SITol)) was prepared, characterized, and tested in the thermally induced ring-opening metathesis polymerization of dicyclopentadiene. In addition, the corresponding tricyclohexylphosphine derivative was investigated for comparison. All compounds were isolated as their trans-dichloro isomers. NMR spectroscopic features as well as structural features are, particularly within the NHC-bearing complexes, very similar, but their polymerization activity at elevated temperatures is distinctly different. While the SIMes derivative shows the desired properties, i.e., latency at room temperature and pronounced polymerization activity at elevated temperature, all other preinitiators do not. The preinitiator featuring the SIPr coligand is the most latent one, needing temperatures > 140 °C to show moderate activity in the polymerization of dicyclopentadiene. Compounds bearing the smaller N-heterocyclic carbene congeners are stable and latent at room temperature, but decompose upon heating, diminishing the polymerization activity at elevated temperatures. Density functional calculations show that the SIMes derivative is the easiest to activate and yields the most stable 14-electron intermediate. Finally calculations reveal a distinct influence of the nature of the N-heterocyclic carbene ligand on the position of the equilibrium of cis- and trans-dichloro isomers of the complexes. While the SIPr and the SIMes derivatives prefer the cis-configuration, all other derivatives favor, at least in solvents with low dielectric constants, the trans

  15. Carbon, chromium and molybdenum contents

    International Nuclear Information System (INIS)

    Sinatora, A; Goldenstein, H.; Mei, P.R.; Albertin, E.; Fuoco, R.; Mariotto, C.L.

    1992-01-01

    This work describes solidification experiments on white cast iron, with 15 and 20% of chromium, 2.3, 3.0 and 3.6 % of carbon and 0.0, 1.5 and 2.5 % of molybdenum in test de samples with 30 mm diameter. Measurements were performed on the austenite and eutectic formation arrests, the number of the eutectic carbide particles relative to the total and the eutectic volumes, and the volume fraction of the primary austenite

  16. Chemistry of Iron N -heterocyclic carbene complexes: Syntheses, structures, reactivities, and catalytic applications

    KAUST Repository

    Riener, Korbinian; Haslinger, Stefan; Raba, Andreas; Hogerl, Manuel Peter; Cokoja, Mirza; Herrmann, Wolfgang A.; Kü hn, Fritz

    2014-01-01

    Iron is the most abundant transition metal in Earth's crust. It is relatively inexpensive, not very toxic, and environmentally benign. Undoubtedly, due to the involvement in a multitude of biological processes, which heavily rely on the rich

  17. N-heterocyclic carbene gold hydroxide complexes as bond activation reagents

    OpenAIRE

    Dupuy, Stéphanie

    2014-01-01

    Although known since the 1930s, organogold chemistry has been dormant until recently, primarily due to preconceptions about the inertness of gold in transformations. However, this last decade has witnessed the emergence of a Golden Age with the development of a wealth of reports on gold in a plethora of reactions. In recent years, the drive for more atom- and step-economical and environmentally friendly reactions has become a field of intense research. In our on-going research on well-defined...

  18. Nasal manifestations in chromium industry workers.

    Science.gov (United States)

    Aiyer, R G; Kumar, Gaurav

    2003-04-01

    People working in mines, plating factories, cement industries are mainly exposed to chrome substances, IIexavalent chromium has been implicated for its toxic effect on the nasal mucosa. Hereby we present a rare study of 28 patients who attended out patient department of Otorhinolaryngology at SSG Hospital, Baroda from a nearby chromium industry. This study aims to present various nasal manifestations of toxic effects of prolonged chromium exposure.

  19. Insights into the catalytic activity of [Pd(NHC)(cin)Cl] (NHC = IPr, IPrCl, IPrBr) complexes in the Suzuki-Miyaura reaction

    KAUST Repository

    Nolan, Steven Patrick; Izquierdo, Frederic; Zinser, Caroline; Minenkov, Yury; Cordes, David; Slawin, Alexandra; Cavallo, Luigi; Nahra, Fady; Cazin, Catherine

    2017-01-01

    The influence of C4,5-halogenation on palladium N-heterocyclic carbene complexes and their activity in the Suzuki-Miyaura reaction have been investigated. Two [Pd(NHC)(cin)Cl] complexes bearing IPrCl and IPrBr ligands were synthesized. After

  20. Synthesis of cis - and trans-diisothiocyanato-bis(NHC) complexes of nickel(II) and applications in the Kumada-Corriu reaction

    KAUST Repository

    Jothibasu, Ramasamy

    2010-09-13

    Metathetical reaction of AgSCN with a series of trans-dihalido-bis(carbene) nickel(II) complexes in CH3CN readily afforded the novel diisothiocyanato-bis(carbene) complexes [Ni(NCS)2(NHC)2] (trans-2a, NHC = 1,3-diisopropylbenzimidazolin-2-ylidene; trans-2b, NHC = 1,3-diisobutylbenzimidazolin-2-ylidene; trans-2c, NHC = 1,3- dibenzylbenzimidazolin-2-ylidene; cis-2d, NHC = 1,3-di(2-propenyl) benzimidazolin-2-ylidene; cis-2e, NHC = 1-propyl-3-methylbenzimidazolin-2- ylidene) as greenish-yellow powders in moderate to good yields. While dihalido-bis(carbene) Ni(II) complexes exclusively form trans-complexes, a trans-cis isomerization occurs upon halido-isothiocyanato exchange with complexes bearing less bulky carbene ligands, i.e., cis-2d/e. DFT calculations indicated that this isomerization can be attributed to a reduced energy difference between trans- and cis-isomers of diisothiocyanato complexes. All complexes have been characterized by multinuclear NMR spectroscopy, ESI mass spectrometry, and X-ray diffraction analysis. A catalytic study revealed that cis-complexes generally exhibit greater activities in the Kumada-Corriu coupling reaction. © 2010 American Chemical Society.

  1. Wet skins tanning with chromium in dense CO2 under pressure

    International Nuclear Information System (INIS)

    Saldinari, L.; Dutel, Ch.; Perre, Ch.

    2000-01-01

    An ancestral gesture steadily improved through the centuries, the transformation of skins into leather includes several stages of which the principal one is tanning. Today, 90 % of the world's leather products are tanned with chromium. However, this stage is an environmental liability, and reducing the volume and chromium content of the waste has become a major issue. A first study on skin degreasing by dense CO 2 helped sharply reduce the volume of the fatty effluents. To replace water by dense CO 2 as the tanning medium was the logical next step. The present study was carried out in cooperation with three tanneries in the Rhone-Alpes-Auvergne area of France and a manufacturer of tanning materials. The difficulty of the study was the chemically opposed character of the two media involved. CO 2 is a non-polar and lipophilic solvent while inorganic chromium is insoluble. The water present in the treated skin is a polar and ionic reaction medium and one of the reagents in tanning chemistry. The mixture of these two partially miscible compounds gives a pH 3 by carbonic acid formation. Tanning is based on the reactivity of collagen, the main component of the skin, with hydroxylated complexes of chromium. Collagen is a protein containing some chemical functions, amines (R-NH 2 ) and carboxylic (R-COOH) for example. These functions impart an amphoteric character to the compound. The WERNER theory of complex salts explains the formation of hydroxylated complexes of chromium and their fixing on the carboxylic functions of collagen by oxolation. pH is the key parameter in tanning. The success of the process demands chromium impregnation without fixing it at a pH lower than 5, and then to fix it by increasing the pH. This opened two alternatives for transferring chromium in the skin: solubilize chromium in CO 2 via soluble organometallic complexes; or put the chromium salt into suspension without solubilizing it. The best results were obtained with the second option, which

  2. Enantioselective [3+3] atroposelective annulation catalyzed by N-heterocyclic carbenes

    KAUST Repository

    Zhao, Changgui

    2018-02-05

    Axially chiral molecules are among the most valuable substrates in organic synthesis. They are typically used as chiral ligands or catalysts in asymmetric reactions. Recent progress for the construction of these chiral molecules is mainly focused on the transition-metal-catalyzed transformations. Here, we report the enantioselective NHC-catalyzed (NHC: N-heterocyclic carbenes) atroposelective annulation of cyclic 1,3-diones with ynals. In the presence of NHC precatalyst, base, Lewis acid and oxidant, a catalytic C–C bond formation occurs, providing axially chiral α-pyrone−aryls in moderate to good yields and with high enantioselectivities. Control experiments indicated that alkynyl acyl azoliums, acting as active intermediates, are employed to atroposelectively assemble chiral biaryls and such a methodology may be creatively applied to other useful NHC-catalyzed asymmetric transformations.

  3. Tuning and Quantifying Steric and Electronic Effects of N-Heterocyclic Carbenes

    KAUST Repository

    Falivene, Laura

    2014-07-12

    This chapter states that the main handles for tuning steric and electronic effects are the substituents on N atoms, the nature of the C4-C5 bridge (either saturated or unsaturated), and the substituents on the C4 and C5 atoms. The initial intuition that steric properties of N-heterocyclic carbenes (NHCs) could be modulated and could impact catalytic behavior stimulated the development of steric descriptors to quantify the steric requirement of different NHCs and, possibly, to compare them with tertiary phosphines. NHCs can be classified as typically strong σ-basic/π-acid ligands, although they have been also shown to exhibit reasonable π-basic properties. This electronic modularity allows NHC ligands to adapt flexibly to different chemical environments represented by a transition metal and the other ligands. © 2014 Wiley-VCH Verlag GmbH & Co. KGaA. All rights reserved.

  4. Cyclometalated Iridium(III) Carbene Phosphors for Highly Efficient Blue Organic Light-Emitting Diodes.

    Science.gov (United States)

    Chen, Zhao; Wang, Liqi; Su, Sikai; Zheng, Xingyu; Zhu, Nianyong; Ho, Cheuk-Lam; Chen, Shuming; Wong, Wai-Yeung

    2017-11-22

    Five deep blue carbene-based iridium(III) phosphors were synthesized and characterized. Interestingly, one of them can be fabricated into deep blue, sky blue and white organic light-emitting diodes (OLEDs) through changing the host materials and exciton blocking layers. These deep and sky blue devices exhibit Commission Internationale de l'Éclairage (CIE) coordinates of (0.145, 0.186) and (0.152, 0.277) with external quantum efficiency (EQE) of 15.2% and 9.6%, respectively. The EQE of the deep blue device can be further improved up to 19.0% by choosing a host with suitable energy level of its lowest unoccupied molecular orbital (LUMO).

  5. Chromium in aqueous nitrate plutonium process streams: Corrosion of 316 stainless steel and chromium speciation

    International Nuclear Information System (INIS)

    Smith, W.H.; Purdy, G.

    1995-01-01

    This study was undertaken to determine if chromium +6 could exist in plutonium process solutions under normal operating conditions. Four individual reactions were studied: the rate of dissolution of stainless steel, which is the principal source of chromium in process solutions; the rate of oxidation of chromium +3 to chromium +6 by nitric. acid; and the reduction of chromium +6 back to chromium +3 by reaction with stainless steel and with oxalic acid. The stainless steel corrosion rate was found to increase with increasing nitric acid concentration, increasing hydrofluoric acid concentration, and increasing temperature. Oxidation of chromium +3 to chromium +6 was negligible at room temperature and only became significant in hot concentrated nitric acid. The rate of reduction of chromium +6 back to chromium +3 by reaction with stainless steel or oxalic acid was found to be much greater than the rate of the reverse oxidation reaction. Based on these findings and taking into account normal operating conditions, it was determined that although there would be considerable chromium in plutonium process streams it would rarely be found in the +6 oxidation state and would not exist in the +6 state in the final process waste solutions

  6. Chromium in aqueous nitrate plutonium process streams: Corrosion of 316 stainless steel and chromium speciation

    International Nuclear Information System (INIS)

    Smith, W.H.; Purdy, G.M.

    1995-01-01

    This study was undertaken to determine if chromium(+6) could exist in plutonium process solutions under normal operating conditions. Four individual reactions were studied: the rate of dissolution of stainless steel, which is the principal source of chromium in process solutions; the rate of oxidation of chromium(+3) to chromium(+6) by nitric acid; and the reduction of chromium(+6) back to chromium(+3) by reaction with stainless steel and with oxalic acid. The stainless steel corrosion rate was found to increase with increasing nitric acid concentration, increasing hydrofluoric acid concentration, and increasing temperature. Oxidation of chromium(+3) to chromium(+6) was negligible at room temperature and only became significant in hot concentrated nitric acid. The rate of reduction of chromium(+6) back to chromium(+3) by reaction with stainless steel or oxalic acid was found to be much greater than the rate of the reverse oxidation reaction. Based on these findings and taking into account normal operating conditions, it was determined that although there would be considerable chromium in plutonium process streams it would rarely be found in the (+6) oxidation state and would not exist in the (+6) state in the final process waste solutions

  7. Calculated electronic structure of chromium surfaces and chromium monolayers on iron

    International Nuclear Information System (INIS)

    Victora, R.H.; Falicov, L.M.

    1985-01-01

    A self-consistent calculation of the magnetic and electronic properties of the chromium (100) and (110) surfaces and of a chromium monolayer on the (100) and (110) iron surfaces is presented. It is found that (i) the (100) chromium surface is ferromagnetic with a greatly enhanced spin polarization (3.00 electrons); (ii) a substantial enhancement of the spin imbalance exists several (>5) layers into the bulk; (iii) the (110) chromium surface is antiferromagnetic with a large (2.31) spin imbalance; (iv) the (100) chromium monolayer on ferromagnetic iron is ferromagnetic, with a huge spin imbalance (3.63), and aligned antiferromagnetically with respect to the bulk iron; (v) the (110) chromium monolayer on ferromagnetic iron is also ferromagnetic, with a spin imbalance of 2.25 and antiferromagnetically aligned to the iron. The spin imbalance of chromium on iron (100) is possibly the largest of any transition-metal system

  8. Roentgenoelectronic investigation into oxidation of iron-chromium and iron-chromium-nickel alloys

    International Nuclear Information System (INIS)

    Akimov, A.G.; Rozenfel'd, I.L.; Kazanskij, L.P.; Machavariani, G.V.

    1978-01-01

    Kinetics of iron-chromium and iron-chromium-nickel alloy oxidation (of the Kh13 and Kh18N10T steels) in oxygen was investigated using X-ray electron spectroscopy. It was found that according to X-ray electron spectra chromium oxidation kinetics in the iron-chromium alloy differs significantly from oxidation kinetics of chromium pattern. Layer by layer X-ray electron analysis showed that chromium is subjected to a deeper oxidation as compared to iron, and accordingly, Cr 2 O 3 layer with pure iron impregnations is placed between the layer of mixed oxide (Fe 3 O 4 +Cr 2 O 3 ) and metal. A model of the iron-chromium alloy surface is suggested. The mixed oxide composition on the steel surface is presented as spinel Fesub(2+x)Crsub(1-x)Osub(y)

  9. Thermodynamic Properties of Chromium Adsorption by Sediments ...

    African Journals Online (AJOL)

    MBI

    2013-06-19

    Jun 19, 2013 ... The adsorption of Chromium from aqueous solution using river Watari sediment as an adsorbent was modeled. The influence of initial ... number of metals, including chromium, copper, nickel and zinc. The ion ... through filter paper to determine the concentration ... liquid and solid phases were separated by.

  10. Chromium tolerance and reduction potential of Staphylococci ...

    African Journals Online (AJOL)

    In order to study the microbiology of chromium tolerance and reduction at a fly ash dumping site in South Africa, 15 core samples were investigated. It was shown that the 30 year old dumping site exhibited high concentrations of Cr (VI) ranging from 1.6 to 9.6 mg/g. From this contaminated fly ash dumping site, 67 chromium ...

  11. REMOVAL OF HEXAVALENT CHROMIUM FROM AQUEOUS ...

    African Journals Online (AJOL)

    a

    be used again to adsorb heavy metal ions. ... Among these heavy metals are chromium, copper and ... poisoning can result from high exposure to hexavalent chromium [2]. Most of the ..... At low pH, the sorbent is positively charged because of.

  12. Selective and sensitive detection of chromium(VI) in waters using electrospray ionization mass spectrometry.

    Science.gov (United States)

    Weldy, Effie; Wolff, Chloe; Miao, Zhixin; Chen, Hao

    2013-09-01

    From 2000 through 2011, there were 14 criminal cases of violations of the Clean Water Act involving the discharge of chromium, a toxic heavy metal, into drinking and surface water sources. As chromium(VI), a potential carcinogen present in the environment, represents a significant safety concern, it is currently the subject of an EPA health risk assessment. Therefore, sensitive and selective detection of this species is highly desired. This study reports the analysis of chromium(VI) in water samples by electrospray ionization mass spectrometry (ESI-MS) following its reduction and complexation with ammonium pyrrolidinedithiocarbamate (APDC). The reduction and subsequent complexation produce a characteristic [Cr(III)O]-PDC complex which can be detected as a protonated ion of m/z 507 in the positive ion mode. The detection is selective to chromium(VI) under acidic pH, even in the presence of chromium(III) and other metal ions, providing high specificity. Different water samples were examined, including deionized, tap, and river waters, and sensitive detection was achieved. In the case of deionized water, quantification over the concentration range of 3.7 to 148ppb gave an excellent correlation coefficient of 0.9904 using the enhanced MS mode scan. Using the single-reaction monitoring (SRM) mode (monitoring the characteristic fragmentation of m/z 507 to m/z 360), the limit of detection (LOD) was found to be 0.25ppb. The LOD of chromium(VI) for both tap and river water samples was determined to be 2.0ppb. A preconcentration strategy using simple vacuum evaporation of the aqueous sample was shown to further improve the ESI signal by 15 fold. This method, with high sensitivity and selectivity, should provide a timely solution for the real-world analysis of toxic chromium(VI). Copyright © 2012 Forensic Science Society. Published by Elsevier Ireland Ltd. All rights reserved.

  13. Electronic Excitations in Fischer-Type Cr and W Aminocarbene Complexes: A Combined ab Initio and Experimental Study

    Czech Academy of Sciences Publication Activity Database

    Kvapilová, Hana; Hoskovcová, Irena; Kayanuma, M.; Daniel, CH.; Záliš, Stanislav

    2013-01-01

    Roč. 117, č. 45 (2013), s. 11456-11463 ISSN 1089-5639 R&D Projects: GA MŠk LD11086 Institutional support: RVO:61388955 Keywords : METAL CARBENE COMPLEXES * FLASH-PHOTOLYSIS * BASIS-SETS Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.775, year: 2013

  14. M(0) - Aminocarbene complexes (M = Cr, W, Fe): Redox Behavior Tuned by Metal and/or ligand modification

    Czech Academy of Sciences Publication Activity Database

    Hoskovcová, I.; Roháčová, J.; Dvořák, D.; Ludvík, Jiří

    2006-01-01

    Roč. 2, č. 23 (2006), s. 87-95 ISSN 1938-5862 R&D Projects: GA ČR GA203/04/0487 Institutional research plan: CEZ:AV0Z40400503 Keywords : carbene complexes * electrochemistry Subject RIV: CG - Electrochemistry

  15. Peat and coconut fiber as biofilters for chromium adsorption from contaminated wastewaters.

    Science.gov (United States)

    Henryk, Kołoczek; Jarosław, Chwastowski; Witold, Żukowski

    2016-01-01

    Batch adsorption experiments were performed for the removal of chromium (III) and chromium (VI) ions from aqueous solutions using Canadian peat and coconut fiber. The Langmuir model was used to describe the adsorption isotherm. The maximum adsorption for peat reached 18.75 mg/g for Cr(III) and 8.02 mg/g for Cr(VI), whereas the value for fiber was slightly higher and reached 19.21 mg/g for Cr(III) and 9.54 mg/g for Cr(VI). Both chromium forms could be easily eluted from the materials. The adsorption of chromium forms to organic matter could be explained in terms of formation of donor-acceptor chemical covalent bound with hydroxyl groups as ligands and chromium as the central atom in the formed complex. The chromate-reducing activities were monitored with the use of electron paramagnetic resonance spectroscopy. The results showed that both adsorption and reduction occurred simultaneously and the maximum adsorption capacity of hexavalent chromium being equal to 95% for fiber and 92% for peat was obtained at pH 1.5. The reduction of Cr(VI) in wastewaters began immediately and disappeared after 20 h. Both materials contained yeast and fungi species which can be responsible for reduction of chromium compounds, due to their enzymatic activity (Chwastowski and Koloczek (Acta Biochim Pol 60: 829-834, 2013)). The reduction of Cr(VI) is a two-phase process, the first phase being rapid and based on chemical reaction and the second phase having biological features. After the recovery step, both types of organic materials can be used again for chromium adsorption without any loss in the metal uptake. Both of the materials could be used as biofilters in the wastewater treatment plants.

  16. N-Heterocyclic Carbene-Catalyzed Vinylogous Mukaiyama Aldol Reaction of α-Keto Esters and α-Trifluoromethyl Ketones

    KAUST Repository

    Du, Guang-Fen; Wang, Ying; Xing, Fen; Xue, Mei; Guo, Xu-Hong; Huang, Kuo-Wei; Dai, Bin

    2015-01-01

    © Georg Thieme Verlag Stuttgart · New York · Synthesis 2016. N-Heterocyclic carbene (NHC)-catalyzed vinylogous Mukaiyama aldol reaction of ketones was developed. Under the catalysis of 5 mol% NHC, α-keto esters and α-trifluoromethyl ketones reacted with 2-(trimethysilyloxy)furan efficiently to produce γ-substituted butenolides containing adjacent quaternary and tertiary carbon centers in high yields with good diastereoselectivities.

  17. N-Heterocyclic Carbene-Catalyzed Olefination of Aldehydes with Vinyliodonium Salts To Generate α,β-Unsaturated Ketones.

    Science.gov (United States)

    Rajkiewicz, Adam A; Kalek, Marcin

    2018-04-06

    An organocatalyzed metal-free, direct olefination of aldehydes with vinyliodonium salts has been achieved by an N-heterocyclic carbene-promoted C-H bond activation. The reaction proceeds under very mild conditions, delivering a range of (hetero)aryl-vinyl ketones in good yields. The retention of the double bond configuration is uniformly observed, and the application of 2-methoxyphenyl auxiliary group in iodonium salts secures a complete selectivity of the vinyl transfer.

  18. π-face donation from the aromatic N-substituent of N-heterocyclic carbene ligands to metal and its role in catalysis

    KAUST Repository

    Credendino, Raffaele

    2012-05-16

    In this work, we calculate the redox potential in a series of Ir and Ru complexes bearing a N-heterocyclic carbene (NHC) ligand presenting different Y groups in the para position of the aromatic N-substituent. The calculated redox potentials excellently correlate with the experimental ΔE 1/2 potentials, offering a handle to rationalize the experimental findings. Analysis of the HOMO of the complexes before oxidation suggests that electron-donating Y groups destabilize the metal centered HOMO. Energy decomposition of the metal-NHC interaction indicates that electron-donating Y groups reinforce this interaction in the oxidized complexes. Analysis of the electron density in the reduced and oxidized states of representative complexes indicates a clear donation from the C ipso of the N-substituents to an empty d orbital on the metal. In case of the Ru complexes, this mechanism involves the Ru-alkylidene moiety. All of these results suggest that electron-donating Y groups render the aromatic N-substituent able to donate more density to electron-deficient metals through the C ipso atom. This conclusion suggests that electron-donating Y groups could stabilize higher oxidation states during catalysis. To test this hypothesis, we investigated the effect of differently donating Y groups in model reactions of Ru-catalyzed olefin metathesis and Pd-catalyzed C-C cross-coupling. Consistent with the experimental results, calculations indicate an easier reaction pathway if the N-substituent of the NHC ligand presents an electron-donating Y group. © 2012 American Chemical Society.

  19. Chiral PEPPSI Complexes: Synthesis, Characterization, and Application in Asymmetric Suzuki–Miyaura Coupling Reactions

    KAUST Repository

    Benhamou, Laure

    2014-01-13

    PEPPSI complexes incorporating chiral N-heterocyclic carbene (NHC) ligands based on 2,2-dimethyl-1-(o-substituted aryl)propan-1-amines were synthesized. Two complexes, with one saturated and one unsaturated NHC ligand, were structurally characterized. The chiral PEPPSI complexes were used in asymmetric Suzuki-Miyaura reactions, giving atropisomeric biaryl products in modest to good enantiomeric ratios. © 2013 American Chemical Society.

  20. Chiral PEPPSI Complexes: Synthesis, Characterization, and Application in Asymmetric Suzuki–Miyaura Coupling Reactions

    KAUST Repository

    Benhamou, Laure; Besnard, Cé line; Kü ndig, E. Peter

    2014-01-01

    PEPPSI complexes incorporating chiral N-heterocyclic carbene (NHC) ligands based on 2,2-dimethyl-1-(o-substituted aryl)propan-1-amines were synthesized. Two complexes, with one saturated and one unsaturated NHC ligand, were structurally characterized. The chiral PEPPSI complexes were used in asymmetric Suzuki-Miyaura reactions, giving atropisomeric biaryl products in modest to good enantiomeric ratios. © 2013 American Chemical Society.

  1. In Situ Generated Ruthenium-Arene Catalyst for Photoactivated Ring-Opening Metathesis Polymerization through Photolatent N-Heterocyclic Carbene Ligand.

    Science.gov (United States)

    Pinaud, Julien; Trinh, Thi Kim Hoang; Sauvanier, David; Placet, Emeline; Songsee, Sriprapai; Lacroix-Desmazes, Patrick; Becht, Jean-Michel; Tarablsi, Bassam; Lalevée, Jacques; Pichavant, Loïc; Héroguez, Valérie; Chemtob, Abraham

    2018-01-09

    1,3-Bis(mesityl)imidazolium tetraphenylborate (IMesH + BPh 4 - ) can be synthesized in one step by anion metathesis between the corresponding imidazolium chloride and sodium tetraphenylborate. In the presence of 2-isopropylthioxanthone (sensitizer), an IMes N-heterocyclic carbene (NHC) ligand can be photogenerated under irradiation at 365 nm through coupled electron/proton transfer reactions. By combining this tandem NHC photogenerator system with metathesis inactive [RuCl 2 (p-cymene)] 2 precatalyst, the highly active RuCl 2 (p-cymene)(IMes) complex can be formed in situ, enabling a complete ring-opening metathesis polymerization (ROMP) of norbornene in the matter of minutes at room temperature. To the best of our knowledge, this is the first example of a photogenerated NHC. Its exploitation in photoROMP has resulted in a simplified process compared to current photocatalysts, because only stable commercial or easily synthesized reagents are required. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Carbene Reactions

    DEFF Research Database (Denmark)

    Hoffmann, R. W.; Barth, W.; Carlsen, Lars

    1983-01-01

    The gas-phase thermolysis of the norbornadienespirodithiolane S-oxides (5) and (7) led to benzene, ethylene, and carbon disulphide as the major products, possibly involving carbon disulphide oxides as intermediates. Thermolyses of the related sulphones (9) or (14) led to completely different prod...

  3. Low-chromium reduced-activation chromium-tungsten steels

    Energy Technology Data Exchange (ETDEWEB)

    Klueh, R.L.; Alexander, D.J.; Maziasz, P.J. [Oak Ridge National Lab., TN (United States)

    1996-10-01

    Bainitic microstructures formed during continuous cooling can differ from classical upper and lower bainite formed during isothermal transformation. Two types of non-classical bainite were observed depending on the cooling rate: carbide-free acicular bainite at rapid cooling rates and granular bainite at slower cooling rates. The Charpy impact toughness of the acicular ferrite was found to be considerably better than for the granular bainite. It was postulated that alloying to improve the hardenability of the steel would promote the formation of acicular bainite, just as increasing the cooling rate does. To test this, chromium and tungsten were added to the 2 1/4Cr-2W and 2 1/4Cr-2WV steel compositions to increase their hardenability, and the microstructures and mechanical properties were examined.

  4. Low-chromium reduced-activation chromium-tungsten steels

    International Nuclear Information System (INIS)

    Klueh, R.L.; Alexander, D.J.; Maziasz, P.J.

    1996-01-01

    Bainitic microstructures formed during continuous cooling can differ from classical upper and lower bainite formed during isothermal transformation. Two types of non-classical bainite were observed depending on the cooling rate: carbide-free acicular bainite at rapid cooling rates and granular bainite at slower cooling rates. The Charpy impact toughness of the acicular ferrite was found to be considerably better than for the granular bainite. It was postulated that alloying to improve the hardenability of the steel would promote the formation of acicular bainite, just as increasing the cooling rate does. To test this, chromium and tungsten were added to the 2 1/4Cr-2W and 2 1/4Cr-2WV steel compositions to increase their hardenability, and the microstructures and mechanical properties were examined

  5. The behaviour of chromium in aquatic and terrestrial food chains

    International Nuclear Information System (INIS)

    1975-01-01

    Chromium has been considered both as potential radioactive and conventional pollutant. Chromium-51 is produced by the activation of 50 Cr, which may be present either as a component of steel alloys used in reactors, or in Na 2 CrO 4 added as an anticorrosion agent to the cooling water. Only small amounts of 51 Cr are normally found in the liquid waste of nuclear power plants before discharge into rivers. In exceptional situations, however, as a result of the direct release of cooling waters, the aquatic environments may receive relatively large quantities of 51 Cr. Part of this 51 Cr is adsorbed e.g. to the sediments, but a fraction remains in solution in the river water. Somme accumulation of the radionuclide is observed in fresh water and marine organisms. Therefore, although 51 Cr has a relatively short physical half life (27.8d), it is of interest to acquire better information on its accumulation by different species of fresh water organisms and plants, as well as on its behaviour in soils, in order to evaluate the relative importance of this nuclide in the radioactive contamination of the aquatic and terrestrial food chains. As a related and sometimes associated pollutant, stable chromium is also taken into consideration. This element occurs fairly frequently as an environmental pollutant in many countries, either because of its abundance in soils derived from serpentine or because of its release to the environment from industrial wastes. The sequence of presentation of the experiment data is based on the consecutive steps of the contamination process: aquatic environment, soils, plant link of the food chain. Special attention is paid, in the different chapters, to the behaviour of various chemical forms of chromium and to their distribution in different fractions: soluble in water, adsorbed, precipitated on particles or complexed with organic material

  6. Experimental patch testing with chromium-coated materials

    DEFF Research Database (Denmark)

    Bregnbak, David; Thyssen, Jacob P; Jellesen, Morten Stendahl

    2017-01-01

    Chromium coatings on metal alloys can be decorative, and prevent corrosion and metal ion release. We recently showed that handling of a chromium-containing disc resulted in chromium deposition on the skin. To examine patch test reactivity to chromium-coated discs. We included 15 patients: 10...... chromium-allergic patients, and 5 patients without chromium allergy. All were patch tested with potassium dichromate, cobalt chloride, nickel sulfate, and nine different metallic discs. The chromium-allergic patients were also patch tested with serial dilutions of potassium dichromate. Positive...

  7. Electrochemistry of chromium subgroup transition metal ions in an ambient temperature chloroaluminate molten salt

    International Nuclear Information System (INIS)

    Scheffler, T.B.

    1984-01-01

    The electrochemistry of several chromium subgroup transition metal solutes was studied in the basic AlCl 3 -1-methyl-3-ethylimidazolium chloride (MEIC) ionic liquid at 40.0 0 C by using stationary and rotating disk electrode voltametry, chronoamperometry, coulometry, and UV-vis spectrophotometry. Chromium(III) was present in the melt as the chloro complex [CrCl 6 ] 3- . This complex underwent as essentially irreversible reduction, apparently as a result of slow charge-transfer, to a chromium(II) species at ca. -1.08 V versus an aluminum wire immersed in 66.7 mol % melt. Similar investigations of molybdenum and tungsten were also conducted. Mechanisms are proposed to account for the results

  8. Reproductive toxicological aspects of chromium in males

    International Nuclear Information System (INIS)

    Ernst, E.

    1994-01-01

    To expand our present understanding of the effects of chromium on male fertility a number of studies were designed to achieve this through the use of chromium intoxicated experimental animals and through investigation of sexual hormones and sperm quality in welders. Also in view of the lack of an experimental model for effects of noxious substance on the epididymal spermatozoa the main objectives of the series of studies reviewed here were: A. To establish a model for evaluation of epididymal sperm count and motility in the rat. B. To investigate and compare the effects of tri- and hexavalent chromium on epididymal spermatozoa. Further to describe the effects of low-dose long-time exposure of rats to the most toxicological interesting chromium oxidative state - hexavalent chromium. C. By the use of autoradiography and γ-countinuing to expand the present knowledge on the distribution of chromium in the body with special reference to the male reproductive organs. D. To describe the effects of exposure to hexavalent chromium in welding fume on levels of sexual hormones and semen parameters in welders. (EG)

  9. Chromium in leather footwear-risk assessment of chromium allergy and dermatitis

    DEFF Research Database (Denmark)

    Thyssen, Jacob P; Strandesen, Maria; Poulsen, Pia B

    2012-01-01

    Background. Chromium-tanned leather footwear, which releases >3 ppm hexavalent Cr(VI), may pose a risk of sensitizing and eliciting allergic dermatitis. Objectives. To determine the content and potential release of chromium in leather footwear and to discuss the prevention of chromium contact...... allergy and dermatitis. Methods. Sixty pairs of leather shoes, sandals and boots (20 children's, 20 men's, and 20 women's) were purchased in Copenhagen and examined with X-ray fluorescence spectroscopy. Chromium was extracted according to the International Standard, ISO 17075. The detection level for Cr......(VI) was 3 ppm. Results. Chromium was identified in 95% of leather footwear products, the median content being 1.7% (range 0-3.3%). No association with store category or footwear category was found. A tendency for there to be a higher chromium content in footwear with high prices was shown (p(trend) = 0...

  10. Characteristics of chromium-allergic dermatitis patients prior to regulatory intervention for chromium in leather

    DEFF Research Database (Denmark)

    Bregnbak, David; Thyssen, Jacob P; Zachariae, Claus

    2014-01-01

    BACKGROUND: Chromium-tanned leather articles currently constitute the most important cause of contact allergy to chromium in Denmark. A regulation on the content of hexavalent chromium in leather was adopted in November 2013 by the EU member states. OBJECTIVES: To characterize patients...... with chromium allergy and their disease, to serve as a baseline for future studies on the potential effect of the new regulation on chromium in leather. METHODS: A questionnaire case-control study was performed on 155 dermatitis patients with positive patch test reactions to potassium dichromate and a matched...... control group of 621 dermatitis patients. Comparisons were made by use of a χ(2) -test and the Mann-Whitney U-test. Logistic regression analyses were used to test for associations. RESULTS: Sixty-six per cent of chromium-allergic patients had a positive history of contact dermatitis caused by leather...

  11. Leaching of chromium from chromium contaminated soil: Speciation study and geochemical modeling

    Directory of Open Access Journals (Sweden)

    Anđelković Darko H.

    2012-01-01

    Full Text Available Distribution of chromium between soil and leachate was monitored. A natural process of percolating rainwater through the soil was simulated in the laboratory conditions and studied with column leaching extraction. Migration of chromium in the soil is conditioned by the level of chromium soil contamination, the soil organic matter content, and rainwater acidity. Chromium (III and chromium(VI were determined by spectrophotometric method with diphenilcarbazide in acidic media. Comparing the results of chromium speciation in leachate obtained by experimental model systems and geochemical modelling calculations using Visual MINTEQ model, a correlation was observed regarding the influence of the tested parameters. Leachate solutions showed that the concentration of Cr depended on the organic matter content. The influence of pH and soil organic matter content is in compliance after its definition through experimental and theoretical way. The computer model - Stockholm Humic Model used to evaluate the leaching results corresponded rather well with the measured values.

  12. The fate of chromium during tropical weathering

    DEFF Research Database (Denmark)

    Berger, Alfons; Frei, Robert

    2014-01-01

    We performed a mineral, geochemical and Cr–Sr–Pb isotope study on a laterite profile developed on ca. 540 Ma old tonalitic bedrock in Madagascar with special emphasis on the behavior of chromium during tropical weathering. The observed strong depletions of Ca, Si, and P, and enrichment of Fe and Al...... of a former, positively fractionated and mobile chromium pool has been experimentally constrained in circumneutral and basic leachates of powdered tonalite bedrock where δ53Cr of + 0.21 to + 0.48‰ was measured. Our results show that mobilization of chromium is effective under highly oxidative conditions...

  13. A study of the behavior of a cathode film formed in chromium plating with radioactive tracers

    International Nuclear Information System (INIS)

    Yoshida, Katsuyoshi; Suzuki, Akihira; Doi, Kazuyuki; Arai, Katsutoshi

    1979-01-01

    The behavior and composition of a cathode film formed on a steel cathode during chromium plating were studied with radioactive tracers. A special cell with a rapid washing compartment was used for preventing the cathode film from dissolving in electrolyte after plating. The cathode film was composed of two layers. The outer layer facing to the electrolyte had a loose structure and contained more sulfuric anions than the inner layer, for sulfuric acid probably concentrated in the outer layer. This outer layer is called L-film in this paper. The L-film was easily dissolved in the electrolyte solution. The inner layer (called C-film, compact film) was stable against electrolytes and contained less anions than that of L-film. The C-film had a thickness equivalent to 5 mg/m 2 and the concentration of anions unaffected by the composition of electrolytes. The C-film was not reduced to metallic chromium, but it remained in the cathode film during and after plating. This suggests that chromic acid in the cathode film is not reduced to metallic chromium, that metallic chromium is deposited from chromium complexes reaching the cathode surface through the cathode film, and that the complexes do not play a role on the construction of the cathode film. (author)

  14. A novel solid phase extraction procedure on Amberlite XAD-1180 for speciation of Cr(III), Cr(VI) and total chromium in environmental and pharmaceutical samples

    International Nuclear Information System (INIS)

    Narin, Ibrahim; Kars, Ayse; Soylak, Mustafa

    2008-01-01

    Due to the toxicity of chromium, species depend on their chemical properties and bioavailabilities, speciation of chromium is very important in environmental samples. A speciation procedure for chromium(III), chromium(VI) and total chromium in environmental samples is presented in this work, prior to flame atomic absorption spectrometric determination of chromium. The procedure is based on the adsorption of Cr(III)-diphenylcarbazone complex on Amberlite XAD-1180 resin. After oxidation of Cr(III), the developed solid phase extraction system was applied to determinate the total chromium. Cr(III) was calculated as the difference between the total Cr content and the Cr(VI) content. The analytical conditions for the quantitative recoveries of Cr(VI) on Amberlite XAD-1180 resin were investigated. The effects of some alkaline, earth alkaline, metal ions and also some anions were also examined. Preconcentration factor was found to be 75. The detection limits (LOD) based on three times sigma of the blank (N: 21) for Cr(VI) and total chromium were 7.7 and 8.6 μg/L, respectively. Satisfactory results for the analysis of total chromium in the stream sediment (GBW7310) certified reference material for the validation of the presented method was obtained. The procedure was applied to food, water and pharmaceutical samples successfully

  15. Synthesis and reactions of cyclovalence isomers of azo-keto-carbenes

    International Nuclear Information System (INIS)

    Rettenbacher, A.S.

    2001-09-01

    Novel types of cycloaddition products with an azomethine imine functionality have been prepared from ω-azo-α'-diazo ketones with a carbon chain of variable length between the azo- and the keto-group; the reaction is induced by catalytical amounts of rhodium(II) acetate and occurs with the concomitant extrusion of dinitrogen. The synthesis of these cyclic azomethine imines succeeded in the course of the intramolecular reaction of the azo nitrogen atoms with a carbene/carbenoid carbon atom, in situ generated from the α-diazoketone functionality; this is a novel cyclization reaction. Some of the resulting cyclization products are stable and have been isolated, others could only be trapped with dipolarophiles as [3+2] cycloadducts. The ring-size of the heterocyclic products depends on the one hand on the length of the carbon-chain (for n = 0, 1, 2) between the carbonyl carbon atom and the quaternary aliphatic or aromatic carbon atom that blocks the tautomerization of the azo-group in the starting material. On the other hand, the ring size depends on which of the two nitrogen atoms of the azo-group undergoes the ring closure with the carbene/carbenoid carbon atom generated from the α-diazoketon functionality in the course of the reaction. By far the most serious problem in the preparation of the cyclic azomethine imines is the synthesis of the required ω-azo-α'-diazo ketones. A so far unknown property of the azo-group is its intramolecularly directed nucleophilicity toward ketenes, which emerge from acid chlorides and anhydrides, or from α-diazo ketones in the course of the Wolff rearrangement. This complicated the approach to the required ω-azo-α'-diazo ketones via these functionalities as precursors and with the desired chain length between the azo- and diazo-keto-groups. Nevertheless, these problems could be overcome by using alternative strategies. Utilizing ω-azo-α'-diazo ketones a largely commonly applicable approach to endocyclic and N

  16. Experimental patch testing with chromium-coated materials.

    Science.gov (United States)

    Bregnbak, David; Thyssen, Jacob P; Jellesen, Morten S; Zachariae, Claus; Johansen, Jeanne D

    2017-06-01

    Chromium coatings on metal alloys can be decorative, and prevent corrosion and metal ion release. We recently showed that handling of a chromium-containing disc resulted in chromium deposition on the skin. To examine patch test reactivity to chromium-coated discs. We included 15 patients: 10 chromium-allergic patients, and 5 patients without chromium allergy. All were patch tested with potassium dichromate, cobalt chloride, nickel sulfate, and nine different metallic discs. The chromium-allergic patients were also patch tested with serial dilutions of potassium dichromate. Positive/weaker reactions were observed to disc B (1 of 10), disc C (1 of 10), and disc D, disc E, and disc I (4 of 10 each). As no controls reacted to any of the discs, the weak reactions indicate allergic reactions. Positive patch test reactions to 1770 ppm chromium(VI) in the serial dilutions of potassium dichromate were observed in 7 of 10 patients. When the case group was narrowed down to include only the patients with a current positive patch test reaction to potassium dichromate, elicitation of dermatitis by both chromium(III) and chromium(VI) discs was observed in 4 of 7 of patients. Many of the patients reacted to both chromium(III) and chromium(VI) surfaces. Our results indicate that both chromium(VI) and chromium(III) pose a risk to chromium-allergic patients. © 2017 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  17. Reaction of Oxygen with Chromium and Chromium Carbide at Low O2 Pressures and High Temperatures

    International Nuclear Information System (INIS)

    Hur, Dong O.; Kang, Sung G.; Paik, Young N.

    1984-01-01

    The oxidation rate of chromium carbide has been measured continuously using thermogravimetric analysis at different oxygen pressures ranging from 1.33x10 -2 to 2.67x10 -1 Pa O 2 at 1000-1300 .deg. C. The oxidation of pure chromium has also been studied between 1000-1300 .deg. C under 6.67x10 -2 Pa O 2 and compared with that of chromium carbide. The oxidation of chromium carbide showed a linear behavior which was different from that of chromium. The oxidation rate of chromium carbide increased with increasing temperature and oxygen pressure was lower than of pure chromium. Above 1200 .deg. C, the volatile oxide was formed and evaporated causing a weight loss. The compositions and morphology of the oxide were studied with X-ray diffractometer and scanning electron microscope, respectively. The morphology of oxide changed with varying temperature and pressure. The oxide scale was consisted of mainly two different layers of Cr 2 O 3 and CrO, and the properties of oxide scale were correlated with oxidation behavior. The oxide film formed in the above test condition has been detached from the carbide surface. The crack and pore were thought to be from CO gas evolving at the interface of chromium carbide and its oxide and the major factor of the linear behavior of chromium carbide

  18. Sorption of chromium(III) and chromium(VI) on lead sulfide

    International Nuclear Information System (INIS)

    Music, S.

    1985-01-01

    The sorption of chromium(III) and chromium(VI) on lead sulfide was investigated in dependence on pH, time of sorption, and on the concnetrations of sorbate and sorbent. The mechanisms of the sorption of Crsup(3+) and CrOsub(4)sup(2-) traces on lead sulfide are discussed; a difference between CrOsub(4)sup(2-) sorption on PbS and α-Fesub(2)Osub(3) was found. Sulfates and molybdates affect the removal of chromates from aqueous solutions. Lead sulfide carrier prepared in this work was also used for the preconcentration of chromium(III) and chromium(VI) from tap water. (author)

  19. Determination of chromium(III) and total chromium in marine waters

    Energy Technology Data Exchange (ETDEWEB)

    Gardner, M J [WRc, Henley Road, Medmenham, Marlow SL7 2HD (United Kingdom); Ravenscroft, J E [WRc, Henley Road, Medmenham, Marlow SL7 2HD (United Kingdom)

    1996-03-01

    The development of an analytical technique is described which may be used to determine chromium, chromium(III) and chromium(VI) in estuarine and coastal waters. The method is based on selective micro-solvent extraction with subsequent GFAAS. The technique has been applied in a major North Sea estuary. The results obtained confirm that thermodynamic factors alone cannot be relied upon to describe the form of chromium in estuaries. Kinetic factors appear to have a strong influence over speciation and lead to the persistence of Cr(III) species in environments where Cr(VI) would be expected to be present. (orig.). With 5 figs., 2 tabs.

  20. Coordination behavior of bis-phenolate saturated and unsaturated N-heterocyclic carbene ligands to zirconium: reactivity and activity in the copolymerization of cyclohexene oxide with CO2.

    Science.gov (United States)

    Lalrempuia, Ralte; Breivik, Frida; Törnroos, Karl W; Le Roux, Erwan

    2017-06-27

    Tetravalent zirconium complexes supported by tridentate bis-phenolate imidazolidin-2-ylidene (L1), imidazol-2-ylidene (L2) and benzimidazol-2-ylidene (L3) NHC ligands were synthesized and evaluated as precursors for the copolymerization of cyclohexene oxide (CHO) with CO 2 . While the reactivity of the imidazolidinium [H 3 L1] chloride salt with Zr(OiPr) 4 (HOiPr), and subsequent ligand exchanges with either (CH 3 ) 3 SiCl or LiOiPr lead to a series of heteroleptic compounds (κ 3 -O,C,O-L1)Zr(X) 2 (THF) (X = Cl, OiPr), both imidazolium [H 3 L2] and benzimidazolium [H 3 L3] chloride salts give a mixture of homoleptic (κ 3 -O,C,O-NHC) 2 Zr and zwitterionic (κ 2 -O,O-HL)ZrCl 2 (OiPr) compounds along with traces or the absence of the heteroleptic intermediate (κ 3 -O,C,O-NHC)Zr(Cl)(OiPr)(THF). Such dissimilar reactivity between the unsaturated and saturated NHC ligands is predominantly ascribed to the increased acidity of azolium salts along with the π-donor strength of the C carbene in L2 and L3-Zr moieties. The reactivity with the more acidic azolium salts (H 3 L2/3) and the destabilized Zr-X trans to NHC carbene bond results in a significant increase in the amount of homoleptic compounds generating HCl. The released HCl reacts preferentially with the heteroleptic intermediates having non-planar NHC ligands (i.e. L2/3) promoting the formation of zwitterionic complexes. The in situ deprotonation of the isolated zwitterionic (κ 2 -O,O-HL3)ZrCl 2 (OiPr) compound by using Ag 2 O gives the homoleptic complex as the major component along with a bimetallic hydroxo-bridged [(κ 3 -O,C,O-L3)Zr(μ-OH)(OiPr)] 2 compound. Of particular interest is that only the heteroleptic NHC-Zr(iv) complexes were identified to be active and highly selective towards the copolymerization of CHO with CO 2 independently of the co-catalysts used (both anionic and neutral) under mild conditions (P CO 2 < 1 bar, T = 60 °C), and gave atactic and completely alternating copolymers in a

  1. Specification for corrosion-resisting chromium and chromium-nickel steel welding rods and bare electrodes - approved 1969

    International Nuclear Information System (INIS)

    Anon.

    1975-01-01

    This specification covers corrosion-resisting chromium and chromium-nickel steel welding rods for use with the atomic hydrogen and gas-tungsten-arc welding processes and bare electrodes for use with the submerged arc and gas metal-arc welding processes. These welding rods and electrodes include those alloy steels designated as corrosion- or heat-resisting chromium and chromium-nickel steels, in which chromium exceeds 4% and nickel does not exceed 50%

  2. A general access to organogold(iii) complexes by oxidative addition of diazonium salts.

    Science.gov (United States)

    Huang, Long; Rominger, Frank; Rudolph, Matthias; Hashmi, A Stephen K

    2016-05-11

    At room temperature under mild photochemical conditions, namely irradiation with a simple blue light LED, gold(i) chloro complexes of both phosphane and carbene ligands in combination with aryldiazonium salts afford arylgold(iii) complexes. With chelating P,N-ligands cationic six- or five-membered chelate complexes were isolated in the form of salts with weakly coordinating counter anions that were brought in from the diazonium salt. With monodentate P ligands or N-heterocyclic carbene ligands and diazonium chlorides neutral arylgold(iii) dichloro complexes were obtained. The coordination geometry was determined by X-ray crystal structure analyses of representative compounds, a cis arrangement of the aryl and the phosphane ligand at the square planar gold(iii) center is observed.

  3. Genesis and transport of hexavalent chromium in the system ophiolitic rocks - groundwater

    Science.gov (United States)

    Shchegolikhina, Anastasia; Guadagnini, Laura; Guadagnini, Alberto

    2015-04-01

    Our study aims at contributing to the quantification and characterization of chromium transport processes from host rocks and soil matrices to groundwater. We focus on dissolved hexavalent chromium detected in groundwaters of geological regions with ophiolitic rocks (ophiolites and serpentinites) inclusions due to its critical ecological impact. (Oze et al., 2004). Despite the large number of analyses on the occurrence of high concentrations of hazardous hexavalent chromium ions in natural waters, only few studies were performed with the objective of identifying and investigating the geochemical reactions which could occur in the natural system rock - groundwater - dissolved chromium (Fantoni et al., 2002, Stephen and James, 2004, Lelli et al., 2013). In this context, there is a need for integration of results obtained from diverse studies in various regions and settings to improve our knowledge repository. Our theoretical analyses are grounded and driven by practical scenarios detected in subsurface reservoirs exploited for civil and industrial use located in the Emilia-Romagna region (Italy). Available experimental datasets are complemented with data from other international regional-scale settings (Altay mountains region, Russia). Modeling of chromium transformation and migration particularly includes characterization of the multispecies geochemical system. A key aspect of our study is the analysis of the complex competitive sorption processes governing heavy metal evolution in groundwater. The results of the research allow assessing the critical qualitative features of the mechanisms of hexavalent chromium ion mobilization from host rocks and soils and the ensuing transformation and migration to groundwater under the influence of diverse environmental factors. The study is then complemented by the quantification of the main sources of uncertainty associated with prediction of heavy metal contamination levels in the groundwater system explored. Fantoni, D

  4. Auxiliary Electrodes for Chromium Vapor Sensors

    Energy Technology Data Exchange (ETDEWEB)

    Fergus, Jeffrey; Shahzad, Moaiz; Britt, Tommy

    2018-05-15

    Measurement of chromia-containing vapors in solid oxide fuel cell systems is useful for monitoring and addressing cell degradation caused by oxidation of the chomia scale formed on alloys for interconnects and balance-of-plant components. One approach to measuring chromium is to use a solid electrolyte with an auxiliary electrode that relates the partial pressure of the chromium containing species to the mobile species in the electrolyte. One example is YCrO3 which can equilibrate with the chromium containing vapor and yttrium in yttria stabilized zirconia to establish an oxygen activity. Another is Na2CrO4 which can equilibrate with the chromium-containing vapor to establish a sodium activity.

  5. Acute and chronic systemic chromium toxicity.

    Science.gov (United States)

    Gad, S C

    1989-10-01

    Although chromium and compounds containing it have been recognized as having potential severe adverse effects on health for more than 160 years, understanding of the systemic toxicology and true hazard of these compounds is still not complete. A review of the current state of knowledge is attempted in this paper, with appropriate attention given to the complications of multiple valence states and solubility. Selected chromium compounds, particularly hexavalent ones, are carcinogens, corrosives, delayed contact sensitizers, and have the kidney as their primary target organ. But chromium is also an essential element for humans. The body clearly possesses some effective detoxification mechanisms for some degree of exposure to hexavalent chrome compounds. The significant features of acute and chronic chromium toxicity are presented in view of these considerations.

  6. 29 CFR 1910.1026 - Chromium (VI).

    Science.gov (United States)

    2010-07-01

    ... allows employees to consume food or beverages at a worksite where chromium (VI) is present, the employer... effect on productivity. 2. Plating Bath Surface Tension Management and Fume Suppression • Lower surface...

  7. Ductile-brittle transition of thoriated chromium.

    Science.gov (United States)

    Wilcox, B. A.; Veigel, N. D.; Clauer, A. H.

    1972-01-01

    Unalloyed chromium and chromium containing approximately 3 wt % ThO2 were prepared from powder produced by a chemical vapor deposition process. When rolled to sheet and tested in tension, it was found that the thoriated material had a lower ductile-to-brittle transition temperature (DBTT) than unalloyed chromium. This ductilizing was evident both in the as-rolled condition and after the materials had been annealed for 1 hour at 1200 C. The improved ductility in thoriated chromium may be associated with several possible mechanisms: (1) particles may disperse slip, such that critical stress or strain concentrations for crack nucleation are more difficult to achieve; (2) particles may act as dislocation sources, thus providing mobile dislocations in this normally source-poor material, in a manner similar to prestraining; and (3) particles in grain boundaries may help to transmit slip across the boundaries, thus relieving stress concentrations and inhibiting crack nucleation.

  8. Uptake and transport of chromium in plants

    International Nuclear Information System (INIS)

    Ramachandran, V.; D'souza, T.J.; Mistry, K.B.

    1980-01-01

    The uptake of chromium, an important soil and water pollutant, by five different plant species was examined in nutrient culture experiments using chromium-51 as a tracer. The concentration in aerial tissues of both trivalent and hexavalent forms of chromium was the greatest in peas followed by beans, tomato and the cereals over identical uptake periods. The uptake of 51 Cr 3+ was, in general, greater than 51 CrO 4 2- . Studies with bean plants indicated that shoot uptake of both forms of chromium decreased with increasing pH and salt concentration of the external solution. Concentrations of 10 -4 M and 10 -5 M DNP inhibited 51 Cr uptake by bean shoots. (author)

  9. Chemical Speciation of Chromium in Drilling Muds

    International Nuclear Information System (INIS)

    Taguchi, Takeyoshi; Yoshii, Mitsuru; Shinoda, Kohzo

    2007-01-01

    Drilling muds are made of bentonite and other clays, and/or polymers, mixed with water to the desired viscosity. Without the drilling muds, corporations could not drill for oil and gas and we would have hardly any of the fuels and lubricants considered essential for modern industrial civilization. There are hundreds of drilling muds used and some kinds of drilling muds contain chromium. The chemical states of chromium in muds have been studied carefully due to concerns about the environmental influence. However it is difficult to determine the chemical state of chromium in drilling muds directly by conventional analytical methods. We have studied the chemical form of chromium in drilling muds by using a laboratory XAFS system and a synchrotron facility

  10. Effects of histidin-2-ylidene vs. imidazol-2-ylidene ligands on the anticancer and antivascular activity of complexes of ruthenium, iridium, platinum, and gold

    Czech Academy of Sciences Publication Activity Database

    Schmitt, F.; Donnelly, K.; Muenzner, J.K.; Rehm, T.; Novohradský, Vojtěch; Brabec, Viktor; Kašpárková, Jana; Albrecht, M.; Schobert, R.; Mueller, T.

    2016-01-01

    Roč. 163, OCT2016 (2016), s. 221-228 ISSN 0162-0134 R&D Projects: GA ČR(CZ) GA14-21053S Institutional support: RVO:68081707 Keywords : n-heterocyclic carbene * human cancer-cells * metal-complexes Subject RIV: BO - Biophysics Impact factor: 3.348, year: 2016

  11. Enhanced π-Back-Donation as a Way to Higher Coordination Numbers in d10 [M(NHC)n] Complexes: A DFT Study

    NARCIS (Netherlands)

    Nitsch, J.; Wolters, L.P.; Fonseca Guerra, C.; Bickelhaupt, F.M.; Steffen, A.

    2016-01-01

    We aim to understand the electronic factors determining the stability and coordination number of d10 transition-metal complexes bearing N-heterocyclic carbene (NHC) ligands, with a particular emphasis on higher coordinated species. In this DFT study on the formation and bonding of Group 9–12 d10

  12. Enhanced pi-Back-Donation as a Way to Higher Coordination Numbers in d10 [M(NHC)n] Complexes: A DFT Study

    NARCIS (Netherlands)

    Nitsch, J.S.; Wolters, L.P.; Fonseca Guerra, C.; Bickelhaupt, F.M.; Steffen, A.

    2017-01-01

    We aim to understand the electronic factors determining the stability and coordination number of d10 transition-metal complexes bearing N-heterocyclic carbene (NHC) ligands, with a particular emphasis on higher coordinated species. In this DFT study on the formation and bonding of Group 9–12 d10

  13. Unraveling the synthesis of homoleptic [Ag(N,N-diaryl-NHC)2]Y (Y = BF4, PF6) complexes by ball-milling.

    Science.gov (United States)

    Beillard, Audrey; Bantreil, Xavier; Métro, Thomas-Xavier; Martinez, Jean; Lamaty, Frédéric

    2016-11-28

    A user-friendly and general mechanochemical method was developed to access rarely described NHC (N-heterocyclic carbene) silver(i) complexes featuring N,N-diarylimidazol(idin)ene ligands and non-coordinating tetrafluoroborate or hexafluorophosphate counter anions. Comparison with syntheses in solution clearly demonstrated the superiority of the ball-milling conditions.

  14. Hexavalent Chromium reduction by Trichoderma inhamatum

    Energy Technology Data Exchange (ETDEWEB)

    Morales-Battera, L.; Cristiani-Urbina, E.

    2009-07-01

    Reduction of hexavalent chromium [Cr(VI)] to trivalent chromium [Cr(III)] is a useful and attractive process for remediation of ecosystems and industrial effluents contaminated with Cr(VI). Cr(VI) reduction to Cr(II) can be achieved by both chemical and biological methods; however, the biological reduction is more convenient than the chemical one since costs are lower, and sludge is generated in smaller amounts. (Author)

  15. REMOVAL OF HEXAVALENT CHROMIUM FROM DRINKING WATER

    Directory of Open Access Journals (Sweden)

    A. R. Asgari ، F. Vaezi ، S. Nasseri ، O. Dördelmann ، A. H. Mahvi ، E. Dehghani Fard

    2008-10-01

    Full Text Available Removal of chromium can be accomplished by various methods but none of them is cost-effective in meeting drinking water standards. For this study, granular ferric hydroxide was used as adsorbent for removal of hexavalent chromium. Besides, the effects of changing contact time, pH and concentrations of competitive anions were determined for different amounts of granular ferric hydroxide. It was found that granular ferric hydroxide has a high capacity for adsorption of hexavalent chromium from water at pH≤7 and in 90 min contact time. Maximum adsorption capacity was determined to be 0.788 mg Cr+6/g granular ferric hydroxide. Although relatively good adsorption of sulfate and chloride had been specified in this study, the interfering effects of these two anions had not been detected in concentrations of 200 and 400 mg/L. The absorbability of hexavalent chromium by granular ferric hydroxide could be expressed by Freundlich isotherm with R2>0.968. However, the disadvantage was that the iron concentration in water was increased by the granular ferric hydroxide. Nevertheless, granular ferric hydroxide is a promising adsorbent for chromium removal, even in the presence of other interfering compounds, because granular ferric hydroxide treatment can easily be accomplished and removal of excess iron is a simple practice for conventional water treatment plants. Thus, this method could be regarded as a safe and convenient solution to the problem of chromium-polluted water resources.

  16. Permeation of chromium salts through human skin in vitro

    DEFF Research Database (Denmark)

    Gammelgaard, Bente; Fullerton, A; Avnstorp, C

    1992-01-01

    Chromium permeation studies were performed on full thickness human skin in diffusion cells. All samples were analysed for the total chromium content by graphite furnace Zeeman-corrected atomic absorption spectrometry. Some samples were analysed by an ion chromatographic method permitting...... the simultaneous determination of Cr(VI) and Cr(III) as well. The amounts of chromium found in all skin layers were significantly higher when potassium dichromate was applied to the skin compared with chromium chloride or chromium nitrate. Chromium could only be detected in the recipient phase after application...... of the dichromate solution. Chromium skin levels increased with increasing concentrations of applied chromium salts up to 0.034 M Cr. The amount of chromium in recipient phase and skin layers increased with increasing pH when the applied solution contained potassium dichromate. This was ascribed to a decreased skin...

  17. Synthesis of New Chiral Benzimidazolylidene–Rh Complexes and Their Application in Asymmetric Addition Reactions of Organoboronic Acids to Aldehydes

    Directory of Open Access Journals (Sweden)

    Weiping He

    2016-09-01

    Full Text Available A series of novel chiral N-heterocyclic carbene rhodium complexes (NHC–Rh based on benzimidazole have been prepared, and all of the NHC–Rh complexes were fully characterized by NMR and mass spectrometry. These complexes could be used as catalysts for the asymmetric 1,2-addition of organoboronic acids to aldehydes, affording chiral diarylmethanols with high yields and moderate enantioselectivities.

  18. Carbene supported dimer of heavier ketenimine analogue with p and si atoms.

    Science.gov (United States)

    Roy, Sudipta; Dittrich, Birger; Mondal, Totan; Koley, Debasis; Stückl, A Claudia; Schwederski, Brigitte; Kaim, Wolfgang; John, Michael; Vasa, Suresh Kumar; Linser, Rasmus; Roesky, Herbert W

    2015-05-20

    A cyclic alkyl(amino) carbene (cAAC) stabilized dimer [(cAAC)Si(P-Tip)]2 (2) (Tip = 2,4,6-triisopropylphenyl) is reported. 2 can be considered as a dimer of the heavier ketenimine (R2C═C═N-R) analogue. The dark-red rod-shaped crystals of 2 were synthesized by reduction of the precursor, cAAC-dichlorosilylene-stabilized phosphinidene (cAAC)SiCl2→P-Tip with sodium napthalenide. The crystals of 2 are storable at room temperature for several months and stable up to 215 °C under an inert atmosphere. X-ray single-crystal diffraction revealed that 2 contains a cyclic nonplanar four-membered SiPSiP ring. Magnetic susceptibility measurements confirmed the singlet spin ground state of 2. Cyclic voltammetry of 2 showed a quasi-reversible one-electron reduction indicating the formation of the corresponding radical anion 2(•-), which was further characterized by EPR measurements in solution. The electronic structure and bonding of 2 and 2(•-) were studied by theoretical calculations. The experimentally obtained data are in good agreement with the calculated values.

  19. Diminishing Chromium Use on Combined Chromium-Gambier Tanning Process Upon the Characteristics of Tanned Leather

    Directory of Open Access Journals (Sweden)

    A. Kasim

    2014-04-01

    Full Text Available The research was aimed to investigate the influence of minimizing chromium use on combined chromium-gambier process upon the characteristics of tanned leather. At the first stage of tanning process, chromium was used and in the second stage it was replaced by gambier. The raw material used was dried saline-preserved goat skin. The treatments applied on the tanning process were the different concentrations of chromium ranging from the highest level of 6% to the lowest level of 1% which was then re-tanned by using 8% concentration of gambier. The examination parameters included chemical and physical properties as well as visual investigation on the tanned leather in accordance with SNI-06-0463-1989-A. The result showed that the tanning process by using 2% chromium in the first step and 8% gambier in the second step was a treatment combination producing tanned leather that met the standard. The examination on tanned leather resulted from such treatment showed 56.33% rawhide, 17.45% of bound tannin, 31.22% of tanning level, tensile strength 386.30 kg/cm2, flexibility 31.91%, leather width 1.3 mm, density 0.75 g/cm3, the leather was quite elastic with light brownish color. In conclusion, minimizing the use of chromium in the combined tanning process of chromium and gambier can be implemented to the lowest of 2% chromium concentration and 8% gambier in the first and second step, respectively.

  20. Effect and Removal Mechanisms of 6 Different Washing Agents for Building Wastes Containing Chromium

    Directory of Open Access Journals (Sweden)

    Wang Xing-run

    2012-01-01

    Full Text Available With the building wastes contaminated by chromium in Haibei Chemical Plan in China as objects, we studied the contents of total Cr and Cr (VI of different sizes, analyzed the effect of 6 different washing agents, discussed the removal mechanisms of 6 different washing agents for Cr in various forms, and finally selected applicable washing agent. As per the results, particle size had little impact on the contents of total Cr and Cr (VI; after one washing with water, the removal rate of total Cr and Cr (VI was 75% and 78%, respectively, and after the second washing with 6 agents, the removal rate of citric acid was the highest, above 90% for total Cr and above 99% for hexavalent chromium; the pH of building wastes were reduced by citric acid, and under acid condition, hexavalent chromium was reduced to trivalent chromium spontaneously by organic acid, which led to better removal rate of acid soluble Cr and reducible Cr; due to the complexing action, citric acid had best removal rate for oxidizable trivalent chromium. In conclusion, citric acid is the most applicable second washing agent for building wastes.

  1. Rhodium (II) carbene C-H insertion in water and catalyst reuse; Insercao C-H de carbenoides de rodio em agua e reutilizacao do catalisador

    Energy Technology Data Exchange (ETDEWEB)

    Candeias, Nuno R.; Gois, Pedro M.P.; Afonso, Carlos A.M. [Instituto Superior Tecnico, Lisboa (Portugal)]. E-mail: carlosafonso@ist.utl.pt

    2007-07-01

    A five-session laboratory experiment is described for the synthesis of a beta-lactam via Rh(II) catalysed intramolecular C-H insertion of a alpha-diazo-alpha-ethoxycarbonyl acetamide. The metallo-carbene, responsible for the C-H bond activation, was generated from the diazo substrate and the catalyst Rh{sub 2}(OAc){sub 4}. The high stability and solubility of the catalyst and the exclusive C-H insertion of the Rh-carbene allows the synthesis of this important heterocycle in water and the catalyst reutilization. (author)

  2. Carbene Chemistry. I. Stereochemical Integrity at C Alpha in Ketone Tosylhydrazones. II. Hydrogen Migration in 2-Carbena-6,6-Dimethylnorbornane.

    Science.gov (United States)

    1978-02-01

    H20, 10% Na2 CO3 , H20, and dried over MqSO 4 . Yields were typically ca. 75%. "! 33 CARBENE CHEMISTRY PART II. HYDROGEN MIGRATION IN 2-CARBENA-6,6...any a delocaliza- tion. Thus if one assumes a single product determining intermediate, carbene 54 is classical in the usual sense of the word. It has...placed in a refrigerator. The crystalline product was re- crystallized from methanol-O-d/D20 yielding purified tosylhydrazone with mp 156-1580. 58

  3. Application of Chan-Lam cross coupling for the synthesis of N-heterocyclic carbene precursors bearing strong electron donating or withdrawing groups

    Science.gov (United States)

    Huang, Liliang; He, Chengxiang; Sun, Zhihua

    2015-07-01

    Chan-Lam cross coupling allowed efficient synthesis of N,N’-disubstituted ortho-phenylene diamines bearing strong electron donating or withdrawing groups, such as nitro or methoxy groups, with moderate to high yields. These diamines can then be turned into N-heterocyclic carbene precursors after condensation with trimethyl orthoformate. The same strategy can also be utilized for the synthesis of N-monosubstituted aniline derivatives containing a functionalized ortho-aminomethyl group as intermediates for chiral 6-membered ring carbene precursors.

  4. Production of propylene from 1-butene on highly active "bi-functional single active site" catalyst: Tungsten carbene-hydride supported on alumina

    KAUST Repository

    Mazoyer, Etienne

    2011-12-02

    1-Butene is transformed in a continuous flow reactor over tungsten hydrides precursor W-H/Al2O3, 1, giving a promising yield into propylene at 150 °C and different pressures. Tungsten carbene-hydride single active site operates as a "bi-functional catalyst" through 1-butene isomerization on W-hydride and 1-butene/2-butenes cross-metathesis on W-carbene. This active moiety is generated in situ at the initiation steps by insertion of 1-butene on tungsten hydrides precursor W-H/Al2O3, 1 followed by α-H and β-H abstraction. © 2011 American Chemical Society.

  5. Solution-phase synthesis of chromium-functionalized single-walled carbon nanotubes

    KAUST Repository

    Kalinina, Irina V.

    2015-03-01

    The solution phase reactions of single-walled carbon nanotubes (SWNTs) with Cr(CO)6 and benzene-Cr(CO)3 can lead to the formation of small chromium clusters. The cluster size can be varied from less than 1 nm to about 4 nm by increasing the reaction time. TEM images suggest that the clusters are deposited predominantly on the exterior walls of the nanotubes. TGA analysis was used to obtain the Cr content and carbon to chromium ratio in the Cr-complexed SWNTs. It is suggested that the carbon nanotube benzenoid structure templates the condensation of chromium atoms and facilitates the loss of carbon monoxide leading to well defined metal clusters.

  6. Solution-phase synthesis of chromium-functionalized single-walled carbon nanotubes

    KAUST Repository

    Kalinina, Irina V.; Al-Hadeethi, Yas Fadel; Bekyarova, Elena; Zhao, Chao; Wang, Qingxiao; Zhang, Xixiang; Al-Zahrani, Ali; Al-Agel, Faisal Abdulaziz M; Al-Marzouki, Fahad M.; Haddon, Robert C.

    2015-01-01

    The solution phase reactions of single-walled carbon nanotubes (SWNTs) with Cr(CO)6 and benzene-Cr(CO)3 can lead to the formation of small chromium clusters. The cluster size can be varied from less than 1 nm to about 4 nm by increasing the reaction time. TEM images suggest that the clusters are deposited predominantly on the exterior walls of the nanotubes. TGA analysis was used to obtain the Cr content and carbon to chromium ratio in the Cr-complexed SWNTs. It is suggested that the carbon nanotube benzenoid structure templates the condensation of chromium atoms and facilitates the loss of carbon monoxide leading to well defined metal clusters.

  7. Separation of valent forms of chromium (3) and chromium (6) by coprecipitation with iron (3) hydroxide

    International Nuclear Information System (INIS)

    Nazirmadov, B.; Khamidov, B.O.; Egorova, L.A.

    1988-01-01

    Soption 9.62x10 -5 mol/l of 51 Cr radioactive isotope in oxidation states 3 and 6 by iron(3) hydroxide in 1 mol/l of KNO 3 and KCl depending on pH medium is investigated. The region of practically total concentration of Cr(3) and Cr(6 + ) (pH=3-6.5) is determined. The results of spectrophotometric investigations, calculational data on distribution of hydroxocation forms of chromium (3) and of chromium (6) anions and sorption by iron (3) hydroxide permit to characterize sorption of chromium forms in different stages of oxidation. The methods of chromium (3) and chromium (6) separation by coprecipitation of iron (3) hydroxide and their precipitation from it is developed on the above foundation

  8. Oral Chromium Exposure and Toxicity

    Science.gov (United States)

    Sun, Hong; Brocato, Jason

    2015-01-01

    Hexavalent chromium [Cr(VI)] is a known carcinogen when inhaled. However, inhalational exposure to Cr(VI) affects only a small portion of the population, mainly by occupational exposures. In contrast, oral exposure to Cr(VI) is widespread and affects many people throughout the globe. In 2008, the National Toxicology Program (NTP) released a 2-year study demonstrating that ingested Cr(VI) was carcinogenic in rats and mice. The effects of Cr(VI) oral exposure is mitigated by reduction in the gut, however a portion evades the reductive detoxification and reaches target tissues. Once Cr(VI) enters the cell, it ultimately gets reduced to Cr(III), which mediates its toxicity via induction of oxidative stress during the reduction while Cr intermediates react with protein and DNA. Cr(III) can form adducts with DNA that may lead to mutations. This review will discuss the potential adverse effects of oral exposure to Cr(VI) by presenting up-to-date human and animal studies, examining the underlying mechanisms that mediate Cr(VI) toxicity, as well as highlighting opportunities for future research. PMID:26231506

  9. Chromium getter studies in TFTR

    International Nuclear Information System (INIS)

    Dylla, H.F.; LaMarche, P.H.; Blanchard, W.R.

    1986-02-01

    We have studied the effects of the deposition of thin films (approx.0.1 μm) of chromium onto approx.70% of the torus area of the Tokamak Fusion Test Reactor (TFTR). The purpose of these experiments was to test the difference between high surface coverage and high pumping speed gettering schemes with respect to minimizing oxygen impurity generation in high power tokamak discharges. The initial Cr deposition had significant effects on vessel outgassing and subsequent plasma performance: the outgassing of H 2 O, CO, and CO 2 decreased by a factor of ten, oxygen impurity radiation decreased by a factor of two, the plasma Z/sub eff/ decreased from 1.3 to 1.1, and the plasma density limit increased by 20%. This improvement correlates with a significant reduction of the edge radiation as the density limit is approached. The effects of the initial and subsequent Cr depositions were relatively long lasting, exhibiting time constants of the order of weeks. We attribute the observed impurity reduction to a modification of the oxide surface on the vessel wall, which is apparently a significant impurity source for oxygen. 17 refs., 6 figs

  10. Chromium-induced skin damage among Taiwanese cement workers.

    Science.gov (United States)

    Chou, Tzu-Chieh; Wang, Po-Chih; Wu, Jyun-De; Sheu, Shiann-Cherng

    2016-10-01

    Little research has been done on the relationships between chromium exposure, skin barrier function, and other hygienic habits in cement workers. Our purpose was to investigate chromium-induced skin barrier disruption due to cement exposure among cement workers. One hundred and eight cement workers were recruited in this study. Urinary chromium concentration was used to characterize exposure levels. The biological exposure index was used to separate high and low chromium exposure. Transepidermal water loss (TEWL) was used to assess the skin barrier function. TEWL was significantly increased in workers with high chromium exposure levels than those with low chromium exposure levels (p = 0.048). A positive correlation was also found between urinary chromium concentration and TEWL (R = 0.28, p = 0.004). After adjusting for smoking status and glove use, a significant correlation between urinary chromium concentrations and TEWL remained. Moreover, workers who smoked and had a high chromium exposure had significantly increased TEWL compared to nonsmokers with low chromium exposure (p = 0.01). Skin barrier function of cement workers may have been disrupted by chromium in cement, and smoking might significantly enhance such skin barrier perturbation with chromium exposure. Decreased chromium skin exposure and smoking cessation should be encouraged at work. © The Author(s) 2015.

  11. Reduction of hexavalent chromium collected on PVC filters.

    Science.gov (United States)

    Shin, Y C; Paik, N W

    2000-01-01

    Chromium exists at various valences, including elemental, trivalent, and hexavalent chromium, and undergoes reduction-oxidation reactions in the environment. Since hexavalent chromium is known as a human carcinogen, it is most important to evaluate the oxidation-reduction characteristics of the hexavalent chromium species. Although hexavalent chromium can be reduced to trivalent state, the detailed information on this in workplace environments is limited. The purpose of this study was to investigate hexavalent chromium reduction in time in various conditions. A pilot chrome plating operation was prepared and operated in a laboratory for this study. There was evidence that the hexavalent chromium was reduced by time after mist generation. The percentage ratio (with 95% confidence intervals in parentheses) of hexavalent chromium to total chromium was almost 100% (99.1 approximately 102.3) immediately after mist generation, and was reduced to 87.4% (84.8 approximately 89.9) at 1 hour and 81.0% (78.3 approximately 83.5) at 2 hours, respectively. Another test indicated that hexavalent chromium collected on PVC filters was also reduced by time after sampling. Hexavalent chromium was reduced to 90.8% (88.2 approximately 93.3) at 2 hours after sampling. It also was found that hexavalent chromium was reduced during storage in air. It is recommended that air samples of hexavalent chromium be protected against reduction during storage.

  12. Synthesis, Structural Analysis and Antimicrobial Activities of Novel Water Soluble Ionic Liquids Derived from N-Heterocyclic Carbene Salts

    Directory of Open Access Journals (Sweden)

    Ahmet Kunduracıoğlu

    2016-06-01

    Full Text Available Six N-heterocyclic Carbene based Ionic Liquids (ILs have been synthesized by conventional methods. The ILs were spectroscopically characterized by NMR and FT-IR techniques. Their in vitro antimicrobial activities were determined towards gram-positive and gram-negative bacterias and yeast strains using minimum inhibition concentration (MIC assay. The best inhibition performances were obtained with compound 1 due to its more hydrophilic nature compared with the others. It exhibited 1 mg L–1 MIC value against to the most bacteria while the others showed 4 mg L–1. This work is licensed under a Creative Commons Attribution 4.0 International License.

  13. A Catalyst-Enabled Diastereodivergent Aza-Diels-Alder Reaction: Complementarity of N-Heterocyclic Carbenes and Chiral Amines.

    Science.gov (United States)

    Rong, Zi-Qiang; Wang, Min; Chow, Chi Hao Eugene; Zhao, Yu

    2016-07-04

    Highly efficient and diastereodivergent aza-Diels-Alder reactions have been developed to access either diastereomeric series of benzofuran-fused δ-lactams and dihydropyridines in nearly perfect stereoselectivity (d.r. >20:1, >99 % ee for all examples). The complementarity of N-heterocyclic carbene and chiral amine as the catalyst was demonstrated for the first time, together with an excellent level of catalytic efficiency (1 mol % loading). © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Synthesis, Characterization and Application of A Novel Carbon Bridged Half-metallocene Chromium Catalyst for Methyl Methacrylate Polymerization

    Institute of Scientific and Technical Information of China (English)

    CHENG Zhengzai; GONG Kai; WANG Yang; ZHOU Xue; ZHANG Weixing; LI Yin; SUN Junquan; LI Wenbing

    2014-01-01

    A new carbon bridged cyclopentadienyl chromium complex of the type [(C5H4)C(CH3)2 CH2(C5H4N)]CrCl2 was prepared by treatment of CrCl3•(THF)3 in THF solution with the lithium salt of ligand containing cyclopentadienyl and pyridyl groups. The chromium complex was characterized by 1H NMR and elemental analysis(EA), and the crystal structure was determined by X-ray diffraction analysis. Activated by Al(i-Bu)3, the chromium complex displayed a very high activity for methyl methacrylate (MMA) polymerization. After 24 hours,more than 95.5%MMA was converted to polymethyl methacrylate (PMMA) with a viscosity average molecular weight (Wη) of 416000 g•mol-1 at 60℃for MMA/Al(i-Bu)3/chromium catalyst molar ratio of up to 2000:20:1. Effects of temperature, molar ratios of MMA/catalyst and catalyst/cocatalyst on the polymerization have been studied. The high conversion of MMA and high molecular weight of PMMA with narrow molecular weight distribution is caused by the unique stable active site formed by the new chromium complex and aluminum cocatalyst.

  15. The enriched chromium neutrino source for GALLEX

    International Nuclear Information System (INIS)

    Hartmann, F.X.; Hahn, R.L.

    1991-01-01

    The preparation and study of an intense source of neutrinos in the form of neutron irradiated materials which are enriched in Cr-50 for use in the GALLEX solar neutrino experiment are discussed. Chromyl fluoride gas is enriched in the Cr-50 isotope by gas centrifugation and subsequently converted to a very stable form of chromium oxide. The results of neutron activation analyses of such chromium samples indicate low levels of any long-lived activities, but show that short-lived activities, in particular Na-24, may be of concern. These results show that irradiating chromium oxide enriched in Cr-50 is preferable to irradiating either natural chromium or argon gas as a means of producing a neutrino source to calibrate the GALLEX detector. These results of the impurity level analysis of the enriched chromyl fluoride gas and its conversion to the oxide are also of interest to work in progress by other members of the Collaboration investigating an alternative conversion of the enriched gas to chromium metal. 35 refs., 12 figs., 5 tabs

  16. Serum chromium levels in gestational diabetes mellitus

    Directory of Open Access Journals (Sweden)

    P G Sundararaman

    2012-01-01

    Full Text Available Objective: To measure serum chromium level in women with gestational diabetes mellitus (GDM from Chennai, South India. Materials and Methods: Thirty women with gestational diabetes, 60 age matched controls. Inclusion criteria: Gestational age 22-28 weeks, age group 20-35 years. Exclusion Criteria: Gestational age beyond 28 weeks, malnutrition or presence of infection. Serum chromium was measured using inductive couple plasma emission spectrometer. Results: Serum chromium levels of women with GDM, 1.59+/-0.02 ng/ml (range: 0.16-4.0 ng/ml were lower than in controls (4.58+/-0.62 ng/ml; range 0.82-5.33 ng/ml (P < 0.001. However, there were no significant differences among cases and controls when subdivided by parity. Conclusions: Women with GDM from a South Indian city had lower levels of serum chromium compared to pregnant women without GDM. Studies may be done whether chromium supplementation is useful in this group of women.

  17. Studies of ion implanted thermally oxidised chromium

    International Nuclear Information System (INIS)

    Muhl, S.

    1977-01-01

    The thermal oxidation of 99.99% pure chromium containing precise amounts of foreign elements has been studied and compared to the oxidation of pure chromium. Thirty-three foreign elements including all of the naturally occurring rare earth metals were ion implanted into chromium samples prior to oxidation at 750 0 C in oxygen. The role of radiation induced damage, inherent in this doping technique, has been studied by chromium implantations at various energies and doses. The repair of the damage has been studied by vacuum annealing at temperatures up to 800 0 C prior to oxidation. Many of the implants caused an inhibition of oxidation, the greatest being a 93% reduction for 2 x 10 16 ions/cm 2 of praseodymium. The distribution of the implant was investigated by the use of 2 MeV alpha backscattering and ion microprobe analysis. Differences in the topography and structure of the chromic oxide on and off the implanted area were studied using scanning electron and optical microscopy. X-ray diffraction analysis was used to investigate if a rare earth-chromium compound of a perovskite-type structure had been formed. Lastly, the electrical conductivity of chromic oxide on and off the implanted region was examined at low voltages. (author)

  18. Effect of chromium toxicity on germination and early seedling growth ...

    African Journals Online (AJOL)

    USER

    2010-07-19

    Jul 19, 2010 ... germination and early seedling growth of melon (Cucumis melo L.). Chromium ... chromium on seed germination and seedling growth- biomass in early ..... such critical regulatory mechanisms are likely to operate in seeds at ...

  19. Stabilization of chromium salt in ordinary portland cement

    Indian Academy of Sciences (India)

    Ordinary Portland cement (OPC) samples containing the chromium salt have been investigated using differential microcalorimetry, conductometry and Fourier transform infrared spectroscopic analysis. The effect of chromium on OPC hydration was evaluated by continuous observing of early hydration.

  20. Chromium: a review of environmental and occupational toxicology.

    Science.gov (United States)

    Bencko, V

    1985-01-01

    The following topics are covered in this brief review on the environmental and occupational toxicology of chromium: occurrence, production and uses of chromium and chromium compounds; experimental toxicology; chromium toxicity for man; hygienic and ecologic aspects of chromium contamination of the environment. The review provides a conclusive evidence which suggests that chromium, especially its hexavalent form, is both toxic and carcinogenic, but its trivalent form is physiologically essential in the metabolism of insulin. It is also emphasized that among the major sources of environmental chromium today are the cement industry and the increasingly widespread use of chromium compounds added as an anticorrosion admixture to a variety of cooling systems, e.g. in large power plants, which may greatly contribute to the overall pollution of outdoor air at the sites.

  1. Chromium: a review of environmental and occupational toxicology

    Energy Technology Data Exchange (ETDEWEB)

    Bencko, V

    1985-01-01

    The following topics are covered in this brief review on the environmental and occupational toxicology of chromium: occurrence, production and uses of chromium and chromium compounds; experimental toxicology; chromium toxicity for man; hygienic and ecologic aspects of chromium contamination of the environment. The review provides a conclusive evidence which suggests that chromium, especially its hexavalent form, is both toxic and carcinogenic, but its trivalent form is physiologically essential in the metabolism of insulin. It is also emphasized that among the major sources of environmental chromium today are the cement industry and the increasingly widespread use of chromium compounds added as an anticorrosion admixture to a variety of cooling systems, e.g. in large power plants, which may greatly contribute to the overall pollution of outdoor air at the sites. 108 references.

  2. Surface Chemistry and Spectroscopy of Chromium in Inorganic Oxides

    NARCIS (Netherlands)

    Weckhuysen, B.M.; Wachs, I.E.; Schoonheydt, R.A.

    1996-01-01

    Focuses on the surface chemistry and spectroscopy of chromium in inorganic oxides. Characterization of the molecular structures of chromium; Mechanics of hydrogenation-dehydrogenation reactions; Mobility and reactivity on oxidic surfaces.

  3. Bioremediation of chromium in tannery effluent by microbial consortia

    African Journals Online (AJOL)

    USER

    2010-05-24

    May 24, 2010 ... Chromium is the most toxic and common among the heavy metal pollutants of industrial effluents .... Chromium (Cleseari and Green, 1995) included the oxidation of .... like uranium in its cells might also match with its tendency.

  4. A pulse radiolysis study of the reaction of hydroxyl radicals with trans-dihydroxo(1,4,8,11-tetraazacyclotetradecane)chromium(3)

    International Nuclear Information System (INIS)

    Moensted, O.; Nord, G.; Pagsberg, P.

    1987-01-01

    Hydroxyl radicals react rapidly with the title chromium(III) complex. In weakly alkaline solution, around pH≅ the product rearranges by a first-order process followed by a second-order process. This sequence is interpreted as the formation of a chromium(IV) complex which then forms a μ-peroxochromium(III) dimer. The dimer decomposes by a two-electron oxidation of the macrocyclic ligan with the concomitant formation of a double bond. In more strongly basic solution and also in dilute acid, the decay kinetics are more complicated. Supplementary measurements using trans-difluoro(1,4,8,11-tetraazacyclotetradecane)Chromium(III), which does not contain coordinated hydroxide, and cis-dihydroxo(rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane)-chromium(III), for which dimerization is sterically hindered, support the above interpretation of the consecutive reactions for the title complex. (author)

  5. Distribuição e biodisponibilidade de crômio em solos contaminados por resíduos de couro Distribution and bioavailability of chromium in contaminated soils by tannery residues

    Directory of Open Access Journals (Sweden)

    Ademir dos Santos

    2009-01-01

    Full Text Available Samples of soil, water and sediment were collected and analyzed in order to evaluate chromium contamination due to deposition of tannery residues onto soils under different management regimes. The results showed that soils used for sugar cane cultivation were not adversely impacted. However, in the case of mango plantations, variable concentrations of chromium were measured in the soil profile, with 22.2% of values being higher than permitted legal limits, and 38.9% being at levels requiring remediation. Concentrations of bioavailable chromium were lower than the detection limit of the method (0.01 mg of chromium kg-1 of soil, indicating that all of the chromium present in the samples was either complexed or in an insoluble form. Chromium concentrations measured in samples of water and sediments were indicative of low mobility of the metal in soils. The main cause of differences found between soil samples obtained from different cultivations was the type of soil management.

  6. N-Heterocyclic Carbene Capture by Cytochrome P450 3A4

    Science.gov (United States)

    Jennings, Gareth K.; Ritchie, Caroline M.; Shock, Lisa S.; Lyons, Charles E.

    2016-01-01

    Cytochrome P450 3A4 (CYP3A4) is the dominant P450 enzyme involved in human drug metabolism, and its inhibition may result in adverse interactions or, conversely, favorably reduce the systemic elimination rates of poorly bioavailable drugs. Herein we describe a spectroscopic investigation of the interaction of CYP3A4 with N-methylritonavir, an analog of ritonavir, widely used as a pharmacoenhancer. In contrast to ritonavir, the binding affinity of N-methylritonavir for CYP3A4 is pH-dependent. At pH UV-visible spectroscopy binding studies with molecular fragments narrows the source of this pH dependence to its N-methylthiazolium fragment. The C2 proton of this group is acidic, and variable-pH resonance Raman spectroscopy tentatively assigns it a pKa of 7.4. Hence, this fragment of N-methylritonavir is expected to be readily deprotonated under physiologic conditions to yield a thiazol-2-ylidene, which is an N-heterocyclic carbene that has high-affinity for and is presumed to be subsequently captured by the heme iron. This mechanism is supported by time-dependent density functional theory with an active site model that accurately reproduces distinguishing features of the experimental UV-visible spectra of N-methylritonavir bound to CYP3A4. Finally, density functional theory calculations support that this novel interaction is as strong as the tightest-binding azaheterocycles found in P450 inhibitors and could offer new avenues for inhibitor development. PMID:27126611

  7. Spectrophotometric determination of chromium in geological samples

    International Nuclear Information System (INIS)

    Rathore, D.P.S.; Tarafder, P.K.

    1992-01-01

    A method for the determination of chromium is presented, based on the oxidation of hydroxylamine hydrochloride to nitrous acid by chromium(VI) in acetic acid medium followed by diazotization of the nitrite produced with p-aminophenylmercaptoacetic acid and subsequent coupling of the diazonium salt with N-(1-naphthyl)ethylenediamine di-hydrochloride in acidic medium to form a stable blueish azo dye. The method is suitable for the determination of chromium(VI) from 0.04 to 1.2 mg l -1 in a 1.0-cm cuvette. The molar absorptivity and Sandell's sensitivity are 3.65x10 4 l mol -1 cm -1 and 0.0014μg cm -2 , respectively. (author). 17 refs.; 3 figs

  8. Hexavalent Chromium IV-Free Primer Development

    Science.gov (United States)

    Alldredge, Michael J.; Buck, Amy L.

    2015-01-01

    Primer materials provide corrosion protection for metal parts as well as an increased adhesion between metallic substrates and thermal protection systems (TPSs). Current primers for use in cryogenic applications contain hexavalent chromium. This hexavalent chromium provides excellent corrosion protection even in a cryogenic environment, but it is a carcinogen that requires special equipment and waste control procedures to use. The hazardous nature of hexavalent chromium makes it an obsolescence risk in the future. This study included two phases of evaluation. Thirteen primers were initially identified as candidates and twelve of those primers were tested in phase 1. Four of the best performing candidates from phase 1 continued into phase 2 testing. Phase 1 testing consisted mostly of liquid constituent and physical property testing. Cryoflex and salt fog testing were included in phase 1 because of their importance to the overall success of a candidate material. Phase 2 consisted of physical, thermal, and mechanical properties for nominally processed and fabricated specimens.

  9. Chromium Stable Isotope Fractionation - An Indicator of Hexavalent Chromium Reduction.

    Science.gov (United States)

    Ellis, A.; Johnson, T. M.; Bullen, T. D.

    2001-12-01

    Chromium is a common anthropogenic contaminant in surface water and ground water, and is also of interest in oceanography. It is redox-active; the two common valences in natural waters are Cr(VI), which is highly soluble and toxic, and Cr(III), which is relatively insoluble. Redox reactions thus control Cr mobility in aqueous solutions, and reduction of Cr(VI) to Cr(III) is the most important reaction controlling attenuation of Cr in groundwater. Our results show that Cr(VI) reduction favors the lighter isotopes and leads to enrichment of heavier isotopes in the remaining Cr(VI). Cr isotope measurements thus show great promise as indicators of Cr(VI) reduction. We report here the first measurements of the magnitude of Cr isotope fractionation during Cr(VI) reduction and variations in δ 53Cr values obtained from three contaminated sites. Experiments were conducted to measure Cr isotope fractionation during Cr(VI) reduction by suspensions of magnetite and unamended sediments from a local pond, Urbana, IL and San Francisco Estuary near Martinez, CA. Suspensions were incubated anaerobically with constant shaking, and complete Cr(VI) reduction occurred within a few days. Cr(VI) from intermediate time points in the experiments was purified via ion exchange and 53Cr/52Cr ratios were measured via TIMS with a double isotope spike. The instantaneous per mil fractionation, ɛ , was calculated assuming a Rayleigh fractionation model. The ɛ for Cr(VI) reduction on magnetite surfaces yielded a fractionation of -3.5 ‰ . The ɛ values for the pond and estuary sediments were -3.5 ‰ and -3.3 ‰ respectively. The size of this Cr isotope fractionation is encouraging, as current precision is 0.2 \\permil. δ 53Cr values in dissolved Cr(VI) from three contaminated sites range from 1.1 ‰ to 5.8 ‰ , suggesting that Cr(VI) reduction has occurred and has induced isotopic fractionation in these settings. δ 53Cr values measured from Cr(VI) in plating baths show little or no

  10. Determination of chromium combined with DNA, RNA and proteins in chromium-rich brewer's yeast by NAA

    International Nuclear Information System (INIS)

    Ding, W.J.; Qian, Q.F.; Hou, X.L.; Feng, W.Y.; Chai, Z.F.

    2000-01-01

    The content of chromium in the DNA, RNA and protein fractions separated from chromium-rich and normal brewer's yeast was determined by neutron activation analysis (NAA). Our results show that the extracted relative amounts and concentrations of DNA, RNA and proteins have no significant difference for two types of yeast, but the chromium content in DNA, RNA and proteins fractions extracted from the chromium-rich yeast are substantially higher than those from the normal. In addition, the concentration of chromium in DNA is much higher than that in RNA and proteins. It is evident that the inorganic chromium compounds can enter the yeast cell during the yeast cultivation in the chromium-containing culture medium and are converted into organic chromium species, which are combined with DNA, RNA and proteins. (author)

  11. Proton-Transfer Polymerization by N-Heterocyclic Carbenes: Monomer and Catalyst Scopes and Mechanism for Converting Dimethacrylates into Unsaturated Polyesters

    KAUST Repository

    Hong, Miao; Tang, Xiaoyan; Falivene, Laura; Caporaso, Lucia; Cavallo, Luigi; Chen, Eugene Y.-X.

    2016-01-01

    as methanol insertion products, RxTPT(MeO/H) (R = MeO, Cl; x = 2, 3), and two free carbenes (catalysts), OMe2TPT and OMe3TPT, have been synthesized, while OMe2TPT(MeO/H) and OMe2TPT have also been structurally characterized. The structure

  12. Production of propylene from 1-butene on highly active "bi-functional single active site" catalyst: Tungsten carbene-hydride supported on alumina

    KAUST Repository

    Mazoyer, Etienne; Szeto, Kaï Chung; Norsic, Sé bastien; Garron, Anthony; Basset, Jean-Marie; Nicholas, Christopher P.; Taoufik, Mostafa

    2011-01-01

    1-Butene is transformed in a continuous flow reactor over tungsten hydrides precursor W-H/Al2O3, 1, giving a promising yield into propylene at 150 °C and different pressures. Tungsten carbene-hydride single active site operates as a "bi

  13. Pull-push mechanism for the 1,2-hydrogen rearrangement of carbenes. Substituent and deuterium isotope effects for thermal decomposition of 1-phenyl-2-diazopropanes

    International Nuclear Information System (INIS)

    Su, D.T.T.; Thornton, E.R.

    1978-01-01

    Intramolecular and intermolecular deuterium isotope effects have been measured for the thermal carbene H rearrangements of three substituted 1-phenyl-2-diazopropanes-1-d in hexane at 25 0 C. The isotope effects, k/sub H//k/sub D/, vary from ca. 1.2 to 1.5, increasing with electron-withdrawing substituents, for the formation of both cis- and trans-β-methylstyrenes. Product ratios were determined for these compounds as well as the corresponding undeuterated ones, permitting calculation of intermolecular primary and secondary isotope effects. In addition, the competition among the cis and trans products and the product of H migration from the terminal methyl group permitted determination of Hammett rho values of ca. -1 for the competition between benzylic and terminal migration. The results strongly indicate a ''pull-push'' mechanism, which can be pictured roughly as electrophilic attack on the C--H bond by the phantom p orbital of the carbene along with backside nucleophilic attack by the carbene unshared electron pair to push the H away and form the π bond. The data are believed to be consistent only with a nonzero barrier for the carbene hydrogen rearrangement

  14. 75 FR 67100 - Superalloy Degassed Chromium From Japan

    Science.gov (United States)

    2010-11-01

    ... Chromium From Japan AGENCY: United States International Trade Commission. ACTION: Institution of a five-year review concerning the antidumping duty order on superalloy degassed chromium from Japan. SUMMARY... order on superalloy degassed chromium from Japan would be likely to lead to continuation or recurrence...

  15. Native Chromium Resistant Staphylococci Species from a Fly Ash ...

    African Journals Online (AJOL)

    Sixty-six chromium-resistant Staphylococci species belonging to S. epidermidis, S. aureus, S. saprophyticus and S. arlettae were previously isolated from a chromium-polluted Fly ash (FA) dumping site in South Africa. However the genetic mechanisms responsible for chromium resistance were not known. Polymerase chain ...

  16. Quantitative determination of chromium in some vegetables in ...

    African Journals Online (AJOL)

    Chromium has been known to be a micronutrient for mammals for more than four decades. Deficiency in the body results to diabetes, infertility and cardiovascular diseases. However, progress in elucidating the role of chromium has proceeded slowly. Recent studies have shown a potential role of chromium in maintaining ...

  17. Assessment of the level of chromium species in the discharged ...

    African Journals Online (AJOL)

    The purpose of this study was to assess the level of chromium species in the discharged effluents of selected tanneries in the Amhara Region; Haik and Debre Berhan tanneries. The level of total chromium, and hexavalent chromium in the discharged effluent of the studied tanneries were determined using the ICP-OES, and ...

  18. 21 CFR 73.2327 - Chromium oxide greens.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Chromium oxide greens. 73.2327 Section 73.2327... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2327 Chromium oxide greens. (a) Identity and specifications. The color additive chromium oxide greens shall conform in identify and specifications to the...

  19. 21 CFR 73.1327 - Chromium oxide greens.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Chromium oxide greens. 73.1327 Section 73.1327... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Drugs § 73.1327 Chromium oxide greens. (a) Identity. (1) The color additive chromium oxide greens is principally chromic sesquioxide (Cr2O3). (2) Color additive...

  20. 21 CFR 73.3111 - Chromium oxide greens.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Chromium oxide greens. 73.3111 Section 73.3111... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Medical Devices § 73.3111 Chromium oxide greens. (a) Identity and specifications. The color additive chromium oxide greens (chromic oxide) (CAS Reg. No. 1308-38-9...

  1. 21 CFR 73.1326 - Chromium hydroxide green.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Chromium hydroxide green. 73.1326 Section 73.1326... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Drugs § 73.1326 Chromium hydroxide green. (a) Identity. (1) The color additive chromium hydroxide green is principally hydrated chromic sesquioxide (Cr2O3·XH2O...

  2. 21 CFR 73.2326 - Chromium hydroxide green.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Chromium hydroxide green. 73.2326 Section 73.2326... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2326 Chromium hydroxide green. (a) Identity and specifications.The color additive chromium hydroxide green shall conform in identity and specifications to the...

  3. Thermodynamic properties of chromium bearing slags and minerals. A review

    Energy Technology Data Exchange (ETDEWEB)

    Xiao Yanping; Holappa, L.

    1996-12-31

    In this report, the thermodynamic properties of chromium bearing slags and minerals were reviewed based on the available information in the literature. It includes the analysing methods for oxidation state of chromium in slags, oxidation state of chromium and activities of chromium oxides in slags and minerals. The phase diagrams of chromium oxide systems and chromium distributions between slag and metal phases are also covered ill this review. Concerning the analysing methods, it was found that most of the available approaches are limited to iron free slag systems and the sample preparation is very sensitive to the analysing results. In silicate slags under reducing atmosphere, divalent and trivalent chromium co-exist in the slags. It is agreed that the fraction of divalent chromium to total chromium increases with higher temperature, lower slag basicity and oxygen potential. For the slags under oxidising atmosphere, trivalent, pentavalent and hexavalent states were reported to be stable. The activities of CrO and CrO{sub 1.5} were concluded to have positive deviation from ideal solution. Slag basicity has a positive effect and temperature has a negative effect on the activities of chromium oxides. The phase diagrams of the Cr-O, binary, and ternary chromium containing oxide systems have been examined systematically. The analysis shows that the data on the quaternary and quinary systems are insufficient, and require further investigation. The most important features of the chromium containing silicate slags are the large miscibility gaps and the stability of the chromite spinel. (orig.) (76 refs.)

  4. Hexavalent and trivalent chromium in leather: What should be done?

    Science.gov (United States)

    Moretto, Angelo

    2015-11-01

    Trivalent chromium compounds are used for leather tanning, and chromium may be released during use of leather goods. In certain instances, small amounts of hexavalent chromium can be formed and released. Both trivalent and hexavalent chromium can elicit allergic skin reaction in chromium sensitised subjects, the latter being significantly more potent. Induction of sensitisation only occurs after exposure to hexavalent chromium. A minority of subjects are sensitised to chromium, and in a fraction of these subjects allergic skin reaction have been described after wearing leather shoes or, less frequently, other leather goods. The evidence that in all these cases the reaction is related to hexavalent chromium is not always strong. The content of hexavalent chromium in leather is regulated in European Union, but rate of release rather than content is relevant for allergic skin reaction. The role of trivalent chromium appear much less relevant if at all. Modern tanning procedure do not pose significant risk due to either hexavalent or trivalent chromium. Dismissing bad quality and worn-off leather goods is relevant in reducing or eliminating the skin reaction. It should also be pointed out that shoe components or substances other than chromium in leather may cause allergic/irritative skin reactions. Copyright © 2015 Elsevier Inc. All rights reserved.

  5. 21 CFR 73.1015 - Chromium-cobalt-aluminum oxide.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Chromium-cobalt-aluminum oxide. 73.1015 Section 73... LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Drugs § 73.1015 Chromium-cobalt-aluminum oxide. (a) Identity. The color additive chromium-cobalt-aluminum oxide is a blue-green pigment obtained by calcining a...

  6. Radiation stability of chromium low alloys

    International Nuclear Information System (INIS)

    Chakin, V.P.; Kazakov, V.A.

    1990-01-01

    Radiation effect on the behaviour of mechanical properties and structure of chromium low alloys such as VKh-2K, KhP-3, VKhM in the wide range of temperatures and neutron fluences is studied. Radiation stability of the alloys is shown to be limited by low-temperature radiation embrittlement (LTRE), caused by radiation hardening as a result of formation of radiation-induced defects such as dislocation loops and vacancy voids in the structure. The methods for prevention LTRE of chromium alloys are suggested. 8 refs.; 8 figs

  7. Protective claddings for high strength chromium alloys

    Science.gov (United States)

    Collins, J. F.

    1971-01-01

    The application of a Cr-Y-Hf-Th alloy as a protective cladding for a high strength chromium alloy was investigated for its effectiveness in inhibiting nitrogen embrittlement of a core alloy. Cladding was accomplished by a combination of hot gas pressure bonding and roll cladding techniques. Based on bend DBTT, the cladding alloy was effective in inhibiting nitrogen embrittlement of the chromium core alloy for up to 720 ks (200hours) in air at 1422 K (2100 F). A significant increase in the bend DBTT occurred with longer time exposures at 1422 K or short time exposures at 1589 K (2400 F).

  8. Chromium speciation in environmental samples using a solid phase spectrophotometric method

    Science.gov (United States)

    Amin, Alaa S.; Kassem, Mohammed A.

    2012-10-01

    A solid phase extraction technique is proposed for preconcentration and speciation of chromium in natural waters using spectrophotometric analysis. The procedure is based on sorption of chromium(III) as 4-(2-benzothiazolylazo)2,2'-biphenyldiol complex on dextran-type anion-exchange gel (Sephadex DEAE A-25). After reduction of Cr(VI) by 0.5 ml of 96% concentrated H2SO4 and ethanol, the system was applied to the total chromium. The concentration of Cr(VI) was calculated as the difference between the total Cr and the Cr(III) content. The influences of some analytical parameters such as: pH of the aqueous solution, amounts of 4-(2-benzothiazolylazo)2,2'-biphenyldiol (BTABD), and sample volumes were investigated. The absorbance of the gel, at 628 and 750 nm, packed in a 1.0 mm cell, is measured directly. The molar absorptivities were found to be 2.11 × 107 and 3.90 × 107 L mol-1 cm-1 for 500 and 1000 ml, respectively. Calibration is linear over the range 0.05-1.45 μg L-1 with RSD of <1.85% (n = 8.0). Using 35 mg exchanger, the detection and quantification limits were 13 and 44 ng L-1 for 500 ml sample, whereas for 1000 ml sample were 8.0 and 27 ng L-1, respectively. Increasing the sample volume can enhance the sensitivity. No considerable interferences have been observed from other investigated anions and cations on the chromium speciation. The proposed method was applied to the speciation of chromium in natural waters and total chromium preconcentration in microwave digested tobacco, coffee, tea, and soil samples. The results were simultaneously compared with those obtained using an ET AAS method, whereby the validity of the method has been tested.

  9. Chromium speciation, bioavailability, uptake, toxicity and detoxification in soil-plant system: A review.

    Science.gov (United States)

    Shahid, Muhammad; Shamshad, Saliha; Rafiq, Marina; Khalid, Sana; Bibi, Irshad; Niazi, Nabeel Khan; Dumat, Camille; Rashid, Muhammad Imtiaz

    2017-07-01

    Chromium (Cr) is a potentially toxic heavy metal which does not have any essential metabolic function in plants. Various past and recent studies highlight the biogeochemistry of Cr in the soil-plant system. This review traces a plausible link among Cr speciation, bioavailability, phytouptake, phytotoxicity and detoxification based on available data, especially published from 2010 to 2016. Chromium occurs in different chemical forms (primarily as chromite (Cr(III)) and chromate (Cr(VI)) in soil which vary markedly in term of their biogeochemical behavior. Chromium behavior in soil, its soil-plant transfer and accumulation in different plant parts vary with its chemical form, plant type and soil physico-chemical properties. Soil microbial community plays a key role in governing Cr speciation and behavior in soil. Chromium does not have any specific transporter for its uptake by plants and it primarily enters the plants through specific and non-specific channels of essential ions. Chromium accumulates predominantly in plant root tissues with very limited translocation to shoots. Inside plants, Cr provokes numerous deleterious effects to several physiological, morphological, and biochemical processes. Chromium induces phytotoxicity by interfering plant growth, nutrient uptake and photosynthesis, inducing enhanced generation of reactive oxygen species, causing lipid peroxidation and altering the antioxidant activities. Plants tolerate Cr toxicity via various defense mechanisms such as complexation by organic ligands, compartmentation into the vacuole, and scavenging ROS via antioxidative enzymes. Consumption of Cr-contaminated-food can cause human health risks by inducing severe clinical conditions. Therefore, there is a dire need to monitor biogeochemical behavior of Cr in soil-plant system. Copyright © 2017 Elsevier Ltd. All rights reserved.

  10. Effect of carbon and silicon on nitrogen solubility in liquid chromium and iron-chromium alloys

    International Nuclear Information System (INIS)

    Khyakkinen, V.I.; Bezobrazov, S.V.

    1986-01-01

    The study is aimed at specifying the role of carbon and silicon in high-chromium melts nitridation processes. It is shown that in high-chromium melts of the Cr-Fe-C system the nitrogen solubility is reduced with the growth of carbon content and in the chromium concentration range of 70-100% at 1873 K and P N 2 =0.1 MPa it is described by the lg[%N] Cr-Fe-C =lg[%N] cr-fe -0.098[%C] equation. While decreasing the temperature the nitrogen solubility in alloys is increased. Silicon essentially decreases the nitrogen solubility in liquid chromium. For the 0-10% silicon concentration range the relation between the equilibrium content of nitrogen and silicon at 1873 K and P N 2 =0.1 MPa is described by the straight line equation [%N] Cr-Si =6.1-0.338 [%Si

  11. Chromium allergy and dermatitis: prevalence and main findings

    DEFF Research Database (Denmark)

    Bregnbak, David; Johansen, Jeanne D.; Jellesen, Morten Stendahl

    2015-01-01

    The history of chromium as an allergen goes back more than a century, and includesan interventional success with national legislation that led to significant changes inthe epidemiology of chromium allergy in construction workers. The 2015 EU Leather Regulation once again put a focus on chromium...... allergy, emphasizing that the investigation of chromium allergy is still far from complete. Our review article on chromium focuses on the allergen’s chemical properties, its potential exposure sources, and the allergen’s interaction with the skin, and also provides an overview of the regulations...

  12. Inserção C-H de carbenóides de ródio em água e reutilização do catalisador Rhodium (II carbene C-H insertion in water and catalyst reuse

    Directory of Open Access Journals (Sweden)

    Nuno R. Candeias

    2007-01-01

    Full Text Available A five-session laboratory experiment is described for the synthesis of a beta-lactam via Rh(II catalysed intramolecular C-H insertion of a alpha-diazo-alpha-ethoxycarbonylacetamide. The metallo-carbene, responsible for the C-H bond activation, was generated from the diazo substrate and the catalyst Rh2(OAc4. The high stability and solubility of the catalyst and the exclusive C-H insertion of the Rh-carbene allows the synthesis of this important heterocycle in water and the catalyst reutilization.

  13. Chromium Tolerance and Bioremoval by Cyanobacteria Isolated ...

    African Journals Online (AJOL)

    Two cyanobacterial species Nostoc calcicola HH-12 and Chroococcus minutus HH-11 isolated from a textile mill oxidation pond were examined individually and as consortium for their chromium(VI) tolerance and bioremoval from aqueous solutions. Both species were tolerant to the metal and showed significant increase ...

  14. Thermodynamic Properties of Chromium Adsorption by Sediments ...

    African Journals Online (AJOL)

    The adsorption of Chromium from aqueous solution using river Watari sediment as an adsorbent was modeled. The influence of initial pH, solution temperature, adsorbent and adsorbate concentrations on the adsorption efficiency was investigated using batch equilibrium assays. From the results obtained for the adsorption ...

  15. The electronic structure of antiferromagnetic chromium

    DEFF Research Database (Denmark)

    Skriver, Hans Lomholt

    1981-01-01

    The author has used the local spin density formalism to perform self-consistent calculations of the electronic structure of chromium in the non-magnetic and commensurate antiferromagnetic phases, as a function of the lattice parameter. A change of a few per cent in the atomic radius brings...

  16. Origin of hexavalent chromium in groundwater

    DEFF Research Database (Denmark)

    Kazakis, N.; Kantiranis, N.; Kalaitzidou, K.

    2017-01-01

    Hexavalent chromium constitutes a serious deterioration factor for the groundwater quality of several regions around the world. High concentrations of this contaminant have been also reported in the groundwater of the Sarigkiol hydrological basin (near Kozani city, NW Greece). Specific interest w...

  17. Chromium fractionation and speciation in natural waters.

    Science.gov (United States)

    Pereira, Catarinie Diniz; Techy, João Gabriel; Ganzarolli, Edgard Moreira; Quináia, Sueli Pércio

    2012-05-01

    It is common for leather industries to dump chromium-contaminated effluent into rivers and other bodies of water. Thus, it is crucial to know the impacts caused by this practice to the environment. A study on chromium partitioning and speciation, with determination at trace levels, was carried out in a potentially contaminated creek. Chromium fractionation and speciation was performed using a flow-injection preconcentration system and detection by flame atomic absorption spectrometry. High levels of this element were found in the particulate material (449-9320 mg kg(-1)), which indicates its compatibility with this fraction. The concentration of Cr(iii) in the water samples collected ranged from 5.2-105.2 μg L(-1). Cr(vi) was always below of the DL (0.3 μg L(-1)). Chromium accumulation observed in the sediment (873-1691 mg kg(-1)) may confirm contamination due to the long term release of contaminated effluents in the creek.

  18. Chromium removal from aqueous media by superparamagnetic ...

    Indian Academy of Sciences (India)

    1. Introduction. Industrial wastewater often contains substantial amount ... sion, it is imperative that industries reduce chromium in their effluents to this ..... in standard Gibb's free energy ( Go), enthalpy ( Ho), ... ideal gas constant and T is temperature. Table 3 dis ... sequence of increase in access to functional groups afforded ...

  19. Defect structure of electrodeposited chromium layers

    International Nuclear Information System (INIS)

    Marek, T.; Suevegh, K.; Vertes, A.; El-Sharif, M.; McDougall, J.; Chisolm, C.U.

    2000-01-01

    Positron annihilation spectroscopy was applied to study the effects of pre-treatment and composition of substrates on the quality and defect structure of electrodeposited thick chromium coatings. The results show that both parameters are important, and a scenario is proposed why the mechanically polished substrate gives more defective film than the electro polished one.

  20. Defect structure of electrodeposited chromium layers

    Energy Technology Data Exchange (ETDEWEB)

    Marek, T. E-mail: marek@para.chem.elte.hu; Suevegh, K.; Vertes, A.; El-Sharif, M.; McDougall, J.; Chisolm, C.U

    2000-06-01

    Positron annihilation spectroscopy was applied to study the effects of pre-treatment and composition of substrates on the quality and defect structure of electrodeposited thick chromium coatings. The results show that both parameters are important, and a scenario is proposed why the mechanically polished substrate gives more defective film than the electro polished one.

  1. Effects of chromium on the immune system.

    Science.gov (United States)

    Shrivastava, Richa; Upreti, R K; Seth, P K; Chaturvedi, U C

    2002-09-06

    Chromium is a naturally occurring heavy metal found commonly in the environment in trivalent, Cr(III), and hexavalent, Cr(VI), forms. Cr(VI) compounds have been declared as a potent occupational carcinogen among workers in chrome plating, stainless steel, and pigment industries. The reduction of Cr(VI) to Cr(III) results in the formation of reactive intermediates that together with oxidative stress oxidative tissue damage and a cascade of cellular events including modulation of apoptosis regulatory gene p53, contribute to the cytotoxicity, genotoxicity and carcinogenicity of Cr(VI)-containing compounds. On the other hand, chromium is an essential nutrient required to promote the action of insulin in body tissues so that the body can use sugars, proteins and fats. Chromium is of significant importance in altering the immune response by immunostimulatory or immunosuppressive processes as shown by its effects on T and B lymphocytes, macrophages, cytokine production and the immune response that may induce hypersensitivity reactions. This review gives an overview of the effects of chromium on the immune system of the body. Copyright 2002 Federation of European Microbiological Societies

  2. Nickel-chromium-silicon brazing filler metal

    Science.gov (United States)

    Martini, Angelo J.; Gourley, Bruce R.

    1976-01-01

    A brazing filler metal containing, by weight percent, 23-35% chromium, 9-12% silicon, a maximum of 0.15% carbon, and the remainder nickel. The maximum amount of elements other than those noted above is 1.00%.

  3. Stabilization of chromium: an alternative to make safe leathers.

    Science.gov (United States)

    Gong, Ying; Liu, Xiaoling; Huang, Li; Chen, Wuyong

    2010-07-15

    In this study, the original causes for hexavalent chromium presence in the leather were first evaluated by ageing of chromium(III) solutions and chrome tanned hide powder (50 degrees C, UV lightening at 340 nm, 0-36 h). The results showed that the trivalent chromium at instable coordination state was easy to convert into hexavalent chromium in high pH environment, and the probability of the oxidation increased in this order: multi-coordinate chromium, mono-coordinate chromium, and free chromium. For this reason, the process for stabilizing chromium in the leather was designed with the specific material, which was mostly consisted of the reducers and the chelating agents. After treated with the developed process, these leathers were aged (50 degrees C, UV irradiance as 0.68 W/m(2) at 340 nm, 0-72 h) to estimate chromium(VI) presence. Hexavalent chromium was not found in these treated leathers even if the leathers were aged for 72 h. Moreover, the physical and mechanical properties for the leathers varied little after treating. In a word, an inherent safe and effective process was proved to avoid the formation of hexavalent chromium in the leather. 2010 Elsevier B.V. All rights reserved.

  4. Development of low-chromium, chromium-tungsten steels for fusion

    International Nuclear Information System (INIS)

    Klueh, R.L.; Alexander, D.J.; Kenik, E.A.

    1995-01-01

    High-chromium (9-12% Cr) Cr-Mo and Cr-W ferritic steels are favored as candidates for fusion applications. In early work to develop reduced-activation steels, an Fe-2.25Cr-2W-0.25V-0.1C steel (designated 2.25Cr-2WV) had better strength than an Fe-9Cr-2W-0.25V-0.07Ta-0.1C (9Cr-2WVTa) steel (compositions are in weight percent). However, the 2.25Cr-2WV had poor impact properties, as determined by the ductile-brittle transition temperature and upper-shelf energy of subsize Charpy impact specimens. Because low-chromium steels have some advantages over high-chromium steels, a program to develop low-chromium steels is in progress. Microstructural analysis indicated that the reason for the inferior impact toughness of the 2.25Cr-2WV was the granular bainite obtained when the steel was normalized. Properties can be improved by developing an acicular bainite microstructure by increasing the cooling rate after austenitization. Alternatively, acicular bainite can be promoted by increasing the hardenability. Hardenability was changed by adding small amounts of boron and additional chromium to the 2.25Cr-2WV composition. A combination of B, Cr, and Ta additions resulted in low-chromium reduced-activation steels with mechanical properties comparable to those of 9Cr-2WVTa. (orig.)

  5. The Chromium is an essential element in the human

    International Nuclear Information System (INIS)

    Alvarado Gamez, A.; Blanco Saenz, R.; Mora Morales, E.

    2002-01-01

    The Chromium is an essential element for human and animals, because it a preponderant function in the insulin metabolism as a glucose tolerance factor (GTF). The deficiency of chromium engenders a deterioration in the glucose metabolism due to bad efficiency of insulin. Because the importance of this element an exhaustive reference review was made and this presents some studies realized in laboratory animals and in human beings where it is prove with resuits the effect of chromium over the improvement of patients with non-insulin dependant diabetes. Three substances are presented as chromium active biological forms: a material rich in chromium known as glucose tolerance factor, chromium picolinate and a substance of low molecular weight LMWCr in its forms of apo and holo that contains chromium and it links the insulin receptor and improves its activity. Also this paper presents information about the condition of diabetes in Costa Rica. (Author) [es

  6. Mechanical-thermal synthesis of chromium carbides

    International Nuclear Information System (INIS)

    Cintho, Osvaldo Mitsuyuki; Favilla, Eliane Aparecida Peixoto; Capocchi, Jose Deodoro Trani

    2007-01-01

    The present investigation deals with the synthesis of chromium carbides (Cr 3 C 2 and Cr 7 C 3 ), starting from metallic chromium (obtained from the reduction of Cr 2 O 3 with Al) and carbon (graphite). The synthesis was carried out via high energy milling, followed by heat-treating of pellets made of different milled mixtures at 800 o C, for 2 h, under an atmosphere of argon. A SPEX CertPrep 8000 Mixer/Mill was used for milling under argon atmosphere. A tool steel vat and two 12.7 mm diameter chromium steel balls were used. The raw materials used and the products were characterized by differential thermal analysis, thermo gravimetric analysis, X-ray diffraction, electronic microscopy and X-ray fluorescence chemical analysis. The following variables were investigated: the quantity of carbon in the mixture, the milling time and the milling power. Mechanical activation of the reactant mixture depends upon the milling power ratio used for processing. The energy liberated by the reduction of the chromium oxide with aluminium exhibits a maximum for milling power ratio between 5:1 and 7.5:1. Self-propagating reaction occurred for all heat-treated samples whatever the carbon content of the sample and the milling power ratio used. Bearing carbon samples exhibited hollow shell structures after the reaction. The level of iron contamination of the milled samples was kept below 0.3% Fe. The self-propagated reaction caused high temperatures inside the samples as it may be seen by the occurrence of spherules, dendrites and whiskers. The carbon content determines the type of chromium carbide formed

  7. Design and performance of chromium mist generator

    Directory of Open Access Journals (Sweden)

    Tirgar Aram

    2006-01-01

    Full Text Available Chromium mist generator is an essential tool for conducting researches and making science-based recommendations to evaluate air pollution and its control systems. The purpose of this research was to design and construct a homogenous chromium mist generator and the study of some effective factors including sampling height and distances between samplers in side-by-side sampling on chromium mist sampling method. A mist generator was constructed, using a chromium electroplating bath in pilot scale. Concentration of CrO3 and sulfuric acid in plating solution was 125 g L-1 and 1.25 g L-1, respectively. In order to create permanent air sampling locations, a Plexiglas cylindrical chamber (75 cm height, 55 cm i.d was installed the bath overhead. Sixty holes were produced on the chamber in 3 rows (each 20. The distance between rows and holes was 15 and 7.5 cm, respectively. Homogeneity and effective factors were studied via side-by-side air sampling method. So, 48 clusters of samples were collected on polyvinyl chloride (PVC filters housed in sampling cassettes. Cassettes were located in 35, 50, and 65 cm above the solution surface with less than 7.5 and/or 7.5-15 cm distance between heads. All samples were analyzed according to the NIOSH method 7600. According to the ANOVA test, no significant differences were observed between different sampling locations in side-by-side sampling (P=0.82 and between sampling heights and different samplers distances (P=0.86 and 0.86, respectively. However, there were notable differences between means of coefficient of variations (CV in various heights and distances. It is concluded that the most chromium mist homogeneity could be obtained at height 50 cm from the bath solution surface and samplers distance of < 7.5 cm.

  8. Excitation of different chromium centres by synchrotron radiation in MgO:Cr single crystals

    Energy Technology Data Exchange (ETDEWEB)

    Shablonin, E. [Institute of Physics, University of Tartu, Ravila Str. 14c, 50411 Tartu (Estonia); Popov, A.I., E-mail: popov@latnet.lv [Institute of Solid State Physics, University of Latvia, Kengaraga 8, Riga LV-1063 (Latvia); Lushchik, A., E-mail: aleksandr.lushchik@ut.ee [Institute of Physics, University of Tartu, Ravila Str. 14c, 50411 Tartu (Estonia); Kotlov, A. [Photon Science at DESY, Notkestrasse 85, 22607 Hamburg (Germany); Dolgov, S. [Institute of Physics, University of Tartu, Ravila Str. 14c, 50411 Tartu (Estonia)

    2015-11-15

    The excitation spectra for the emissions of chromium-containing centres have been measured at 10 K using synchrotron radiation of 4–32 eV in MgO single crystals with different content of Cr{sup 3+} (5–850 ppm) and Ca{sup 2+} impurity ions. Both virgin crystals and the samples preliminarily irradiated with x-rays at 295 K have been studied. The role of complex chromium centres containing two Cr{sup 3+} and a cation vacancy (sometimes nearby a Ca{sup 2+} ion) on the luminescence processes and the transformation/creation of structural defects has been analysed. Such anharmonic complex centres could serve as the seeds for the creation of 3D defects that facilitate the cracking and brittle destruction of MgO crystals under their irradiation with ∼GeV heavy ions providing extremely high excitation density within cylindrical ion tracks.

  9. Chromium supplementation improved post-stroke brain infarction and hyperglycemia.

    Science.gov (United States)

    Chen, Wen-Ying; Mao, Frank Chiahung; Liu, Chia-Hsin; Kuan, Yu-Hsiang; Lai, Nai-Wei; Wu, Chih-Cheng; Chen, Chun-Jung

    2016-04-01

    Hyperglycemia is common after acute stroke and is associated with a worse outcome of stroke. Thus, a better understanding of stress hyperglycemia is helpful to the prevention and therapeutic treatment of stroke. Chromium is an essential nutrient required for optimal insulin activity and normal carbohydrate and lipid metabolism. Beyond its nutritional effects, dietary supplement of chromium causes beneficial outcomes against several diseases, in particular diabetes-associated complications. In this study, we investigated whether post-stroke hyperglycemia involved chromium dynamic mobilization in a rat model of permanent focal cerebral ischemia and whether dietary supplement of chromium improved post-stroke injury and alterations. Stroke rats developed brain infarction, hyperglycemia, hyperinsulinemia, glucose intolerance, and insulin resistance. Post-stroke hyperglycemia was accompanied by elevated secretion of counter-regulatory hormones including glucagon, corticosterone, and norepinephrine, decreased insulin signaling in skeletal muscles, and increased hepatic gluconeogenesis. Correlation studies revealed that counter-regulatory hormone secretion showed a positive correlation with chromium loss and blood glucose increased together with chromium loss. Daily chromium supplementation increased tissue chromium levels, attenuated brain infarction, improved hyperglycemia, and decreased plasma levels of glucagon and corticosterone in stroke rats. Our findings suggest that stroke rats show disturbance of tissue chromium homeostasis with a net loss through urinary excretion and chromium mobilization and loss might be an alternative mechanism responsible for post-stroke hyperglycemia.

  10. Synthesis, structure and DFT conformation analysis of CpNiX(NHC) and NiX2(NHC)2 (X = SPh or Br) complexes

    Science.gov (United States)

    Malan, Frederick P.; Singleton, Eric; van Rooyen, Petrus H.; Conradie, Jeanet; Landman, Marilé

    2017-11-01

    The synthesis, density functional theory (DFT) conformational study and structure analysis of novel two-legged piano stool Ni N-heterocyclic carbene (NHC) complexes and square planar Ni bis-N-heterocyclic carbene complexes, all containing either bromido- or thiophenolato ligands, are described. [CpNi(SPh)(NHC)] complexes were obtained from the neutral 18-electron [CpNiBr(NHC)] complexes by substitution of a bromido ligand with SPh, using NEt3 as a base to abstract the proton of HSPh. The 16-electron biscarbene complexes [Ni(SPh)2{NHC}2] were isolated when an excess of HSPh was added to the reaction mixture. Biscarbene complexes of the type [NiBr2(NHC)2] were obtained in the reaction of NiCp2 with a slight excess of the specific imidazolium bromide salt. The molecular and electronic structures of the mono- and bis-N-heterocyclic carbene complexes have been analysed using single crystal diffraction and density functional theory (DFT) calculations, to give insight into their structural properties.

  11. Oxygen-rich molybdenum and chromium complexes: Synthesis ...

    Indian Academy of Sciences (India)

    Administrator

    with high turnover, but this apart, (3) catalytically reduces water present in organic solvent to dihydrogen while oxidising benzaldehyde and cinnamaldehyde to the respective acids. The same catalyst shows catalase type behaviour bringing out dioxygen from hydrogen peroxide. Reference. 1. Bandyopadhyay R, Biswas S, ...

  12. Guidelines To Select the N-Heterocyclic Carbene for the Organopolymerization of Monomers with a Polar Group

    KAUST Repository

    Falivene, Laura

    2017-02-13

    We report on the DFT stability of zwitterion and spirocycle adducts of five polar monomers with nine N-heterocyclic carbenes (NHC), covering the most typical classes of monomers and NHCs used in organopolymerization. Results indicate that the relative stability of the two adducts is dominated by the singlet-triplet energy gap of the free NHC, with low energy gaps favoring the spirocycle adduct, while high energy gaps favor the zwitterionic adduct. This basic structure/property relationship can be tuned by the hindrance of the NHC and the nature of the monomer. In addition to rationalize existing systems, the 45 NHC/monomer combinations we examined can be used as a guideline to predict the behavior of a new NHC/monomer combination.

  13. Synthesis of a 1-Aryl-2,2-chlorosilyl(phosphasilene Coordinated by an N-Heterocyclic Carbene

    Directory of Open Access Journals (Sweden)

    Andreas Wolfgang Kyri

    2016-09-01

    Full Text Available Phosphasilenes, P=Si doubly bonded compounds, have received considerable attention due to their unique physical and chemical properties. We report on the synthesis and structure of a chlorophosphasilene coordinated by an N-heterocyclic carbene (NHC, which has the potential of functionalization at the Si–Cl moiety. Treatment of a silylphosphine, ArPH–SiCl2RSi (Ar = bulky aryl group, RSi = Si(SiMe33 with two equivalents of Im-Me4 (1,3,4,5-tetramethylimidazol-2-ylidene afforded the corresponding NHC-coordinated phosphasilene, ArP=SiClRSi(Im-Me4 as a stable compound. Bonding properties of the P=Si bond coordinated to an NHC will be discussed on the basis of theoretical calculations.

  14. cis-Difluoridobis(1,10-phenanthroline)chromium(III) perchlorate monohydrate

    DEFF Research Database (Denmark)

    Birk, Torben; Bendix, Jesper; Weihe, Högni

    2008-01-01

    The title complex, [CrF(2)(C(12)H(8)N(2))(2)]ClO(4)·H(2)O, displays a slightly distorted octa-hedral coordination geometry around the central chromium(III) ion. The Cr environment is composed of a cis arrangement of two 1,10-phenanthroline [average Cr(III)-N = 2.0726 (10) Å] and two fluoride [ave...

  15. Synthesis, Structure and Catalytic Activity of NHC-AgICarboxylate Complexes

    KAUST Repository

    Wong, Valerie H. L.; Vummaleti, Sai V. C.; Cavallo, Luigi; White, Andrew J. P.; Nolan, Steven P.; Hii, King Kuok Mimi

    2016-01-01

    A general synthetic route was used to prepare 15 new N-heterocyclic carbene (NHC)–AgI complexes bearing anionic carboxylate ligands [Ag(NHC)(O2CR)], including a homologous series of complexes of sterically flexible ITent ligands, which permit a systematic spectroscopic and theoretical study of the structural and electronic features of these compounds. The complexes displayed a significant ligand-accelerated effect in the intramolecular cyclisation of propargylic amides to oxazolidines. The substrate scope is highly complementary to that previously achieved by NHC–Au and pyridyl–AgI complexes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

  16. Synthesis, Structure and Catalytic Activity of NHC-AgICarboxylate Complexes

    KAUST Repository

    Wong, Valerie H. L.

    2016-08-03

    A general synthetic route was used to prepare 15 new N-heterocyclic carbene (NHC)–AgI complexes bearing anionic carboxylate ligands [Ag(NHC)(O2CR)], including a homologous series of complexes of sterically flexible ITent ligands, which permit a systematic spectroscopic and theoretical study of the structural and electronic features of these compounds. The complexes displayed a significant ligand-accelerated effect in the intramolecular cyclisation of propargylic amides to oxazolidines. The substrate scope is highly complementary to that previously achieved by NHC–Au and pyridyl–AgI complexes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

  17. Electronic Structure and Excited-State Dynamics of an Arduengo-Type Carbene and its Imidazolone Oxidation Product.

    Science.gov (United States)

    Schmitt, Hans-Christian; Flock, Marco; Welz, Eileen; Engels, Bernd; Schneider, Heidi; Radius, Udo; Fischer, Ingo

    2017-03-02

    We describe an investigation of the excited-state dynamics of isolated 1,3-di-tert-butyl-imidazoline-2-ylidene (tBu 2 Im, C 11 H 20 N 2 , m/z=180), an Arduengo-type carbene, by time- and frequency-resolved photoionization using a picosecond laser system. The energies of several singlet and triplet excited states were calculated by time-dependent density functional theory (TD-DFT). The S 1 state of the carbene deactivates on a 100 ps time scale possibly by intersystem crossing. In the experiments we observed an additional signal at m/z=196, that was assigned to the oxidation product 1,3-di-tert-butyl-imidazolone, tBu 2 ImO. It shows a well-resolved resonance-enhanced multiphoton ionization (REMPI) spectrum with an origin located at 36951 cm -1 . Several low-lying vibrational bands could be assigned, with a lifetime that depends strongly on the excitation energy. At the origin the lifetime is longer than 3 ns, but drops to 49 ps at higher excess energies. To confirm formation of the imidazolone we also performed experiments on benzimidazolone (BzImO) for comparison. Apart from a redshift for BzImO the spectra of the two compounds are very similar. The TD-DFT values display a very good agreement with the experimental data. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Production of basic chromium sulfate by using recovered chromium from ashes of thermally treated leather.

    Science.gov (United States)

    Dettmer, Aline; Nunes, Keila Guerra Pacheco; Gutterres, Mariliz; Marcílio, Nilson Romeu

    2010-04-15

    Leather wastes tanned with chromium are generated during the production process of leather, hence the wastes from hand crafted goods and footwear industries are a serious environmental problem. The thermal treatment of leather wastes can be one of the treatment options because the wastes are rich in chromium and can be used as a raw material for sodium chromate production and further to obtain several chromium compounds. The objective of this study was to utilize the chromium from leather wastes via basic chromium sulfate production to be subsequently applied in a hide tanning. The obtained results have shown that this is the first successful attempt to achieve desired base properties of the product. The result was achieved when the following conditions were applied: a molar ratio between sodium sulfite and sodium dichromate equal to 6; reaction time equal to 5 min before addition of sulfuric acid; pH of sodium dichromate solution equal to 2. Summarizing, there is an opportunity to utilize the dangerous wastes and reused them in the production scheme by minimizing or annulling the environmental impact and to attend a sustainable process development concept. 2009 Elsevier B.V. All rights reserved.

  19. Femtosecond laser surface structuring and oxidation of chromium thin coatings: Black chromium

    Energy Technology Data Exchange (ETDEWEB)

    Kotsedi, L., E-mail: Kotsedi@tlabs.ac.za [UNESCO-UNISA Africa Chair in Nanosciences-Nanotechnology, College of Graduate Studies, University of South Africa, Muckleneuk Ridge, P.O. Box 392, Pretoria (South Africa); Nanosciences African Network (NANOAFNET), iThemba LABS-National Research Foundation, 1 Old Faure Road, Somerset West 7129, P.O. Box 722, Somerset West, Western Cape (South Africa); Nuru, Z.Y. [UNESCO-UNISA Africa Chair in Nanosciences-Nanotechnology, College of Graduate Studies, University of South Africa, Muckleneuk Ridge, P.O. Box 392, Pretoria (South Africa); Nanosciences African Network (NANOAFNET), iThemba LABS-National Research Foundation, 1 Old Faure Road, Somerset West 7129, P.O. Box 722, Somerset West, Western Cape (South Africa); Mthunzi, P. [National Laser Centre, Council for Scientific and Industrial Research, 0001 Pretoria (South Africa); Muller, T.F.G. [University of the Western Cape, Physics Department, Bellville, 7535 Cape Town (South Africa); Eaton, S.M. [Physics Department, Politecnico di Milano, Piazza Leonardo Da Vinci, 32, 20133 Milano (Italy); Julies, B. [University of the Western Cape, Physics Department, Bellville, 7535 Cape Town (South Africa); Manikandan, E. [UNESCO-UNISA Africa Chair in Nanosciences-Nanotechnology, College of Graduate Studies, University of South Africa, Muckleneuk Ridge, P.O. Box 392, Pretoria (South Africa); Nanosciences African Network (NANOAFNET), iThemba LABS-National Research Foundation, 1 Old Faure Road, Somerset West 7129, P.O. Box 722, Somerset West, Western Cape (South Africa); Ramponi, R. [Physics Department, Politecnico di Milano, Piazza Leonardo Da Vinci, 32, 20133 Milano (Italy); Maaza, M. [UNESCO-UNISA Africa Chair in Nanosciences-Nanotechnology, College of Graduate Studies, University of South Africa, Muckleneuk Ridge, P.O. Box 392, Pretoria (South Africa); Nanosciences African Network (NANOAFNET), iThemba LABS-National Research Foundation, 1 Old Faure Road, Somerset West 7129, P.O. Box 722, Somerset West, Western Cape (South Africa)

    2014-12-01

    Highlights: • Oxidation of the chromium thin film to chromium oxide by femtosecond laser with a fundamental wavelength of 1064 nm. • Solar absorber from chromium oxide that low percentage reflectance. • Femtosecond laser oxidation, with a de-focused laser. • Chromium oxide formation by femtosecond laser in normal ambient. - Abstract: In view of their potential applications as selective solar absorbers, chromium coatings on float glass substrates were nano/micro structured by femtosecond laser in air. Raman and X-rays diffraction investigations confirmed the formation of an ultra-porous α-Cr{sub 2}O{sub 3} layer at the surface; higher is the input laser power, enhanced is the crystallinity of the α-Cr{sub 2}O{sub 3} layer. The α-Cr{sub 2}O{sub 3} layer with the Cr underneath it in addition to the photo-induced porosity acted as a classical ceramic–metal nano-composite making the reflectance to decrease significantly within the spectral range of 190–1100 nm. The average reflectance decreased from 70 to 2%.

  20. Quaternized wood as sorbent for hexavalent chromium.

    Science.gov (United States)

    Low, K S; Lee, C K; Lee, C Y

    2001-01-01

    The potential of quaternized wood (QW) chips in removing hexavalent chromium from synthetic solution and chrome waste under both batch and continuous-flow conditions was investigated. Sorption was found to be dependent on pH, metal concentration, and temperature. QW chips provide higher sorption capacity and wider pH range compared with untreated wood chips. The equilibrium data could be fitted into the Langmuir isotherm model, and maximum sorption capacities were calculated to be 27.03 and 25.77 mg/g in synthetic chromate solution and chrome waste, respectively. The presence of sulfate in high concentration appeared to suppress the uptake of chromium by QW chips. Column studies showed that bed depth influenced the breakthrough time greatly whereas flow rate of influent had little effect on its sorption on the column.

  1. Reduction of hexavalent chromium by Rhizopus Oryzae

    African Journals Online (AJOL)

    EJIRO

    reduction data and the specific growth rate constant value was calculated as 0.082 and the ... Key words: Hexavalent chromium, Rhizopus Oryzae, leather tanning, Monod and Haldane models. ... composition; Glucose 1 g; K2HPO4 0.5 g; NaCl 0.5 g; MgCl2 1.0 g; ... ficantly, because of the inhibitor role of high concentration.

  2. CHROMIUM(II) AMIDES - SYNTHESIS AND STRUCTURES

    NARCIS (Netherlands)

    EDEMA, JJH; GAMBAROTTA, S; MEETSMA, A; SPEK, AL; SMEETS, WJJ; CHIANG, MY

    1993-01-01

    A novel class of mono- and di-meric chromium(II) amides has been prepared and characterized. Reaction of [CrCl2(thf)2] (thf = tetrahydrofuran) with 2 equivalents of M(NR2) (R = C6H11, Pr(i), Ph, or phenothiazinyl; M = Li or Na) allowed the formation of the homoleptic amides [{Cr(mu-NR2)(NR2)}2] (R =

  3. Determination of chromium in biological matrices by neutron activation

    International Nuclear Information System (INIS)

    McClendon, L.T.

    1978-01-01

    Chromium is recognized to be an essential trace element in several biological systems. It exists in many biological materials in a variety of chemical forms and very low concentration levels which cause problems for many analytical techniques. Both instrumental and destructive neutron activation analysis were used to determine the chromium concentration in Orchard Leaves, SRM 1571, Brewers Yeast, SRM 1569, and Bovine Liver, SRM 1577. Some of the problems inherent with determining chromium in certain biological matrices and the data obtained here at the National Bureau of Standards using this technique are discussed. The results obtained from dissolution of brewers yeast in a closed system as described in the DNAA procedure are in good agreement with the INAA results. The same phenomenon existed in the determination of chromium in bovine liver. The radiochemical procedure described for chromium (DNAA) provides the analyst with a simple, rapid and selective technique for chromium determination in a variety of matrices. (T.G.)

  4. Chromium Enrichment on P11 Ferritic Steel by Pack Cementation

    Directory of Open Access Journals (Sweden)

    Fauzi F. A.

    2016-01-01

    Full Text Available The future thermal power plant is expected to operate at higher temperature to improve its efficiency and to reduce greenhouse gas emission. This target requires better corrosion properties of ferritic steels, which commonly used as materials for superheater and reheater of boiler tubes. In this work, chromium enrichment on the surface of ferritic steel is studied. The deposited chromium is expected to become a reservoir for the formation of chromia protective layer. Chromium was deposited on the substrate of steel by pack cementation process for two hours at the temperature of 850ºC, 950ºC and 1050ºC, respectively. XRD analysis indicated that chromium was successfully deposited at all temperatures. Somehow, SEM cross sectional image showed that continuous layer of chromium was not continuously formed at 850oC. Therefore, this research clarify that chromium enrichment by pack cementation may be conducted at the temperature above 950°C.

  5. Iron -chromium alloys and free surfaces: from ab initio calculations to thermodynamic modeling

    International Nuclear Information System (INIS)

    Levesque, M.

    2010-11-01

    Ferritic steels possibly strengthened by oxide dispersion are candidates as structural materials for generation IV and fusion nuclear reactors. Their use is limited by incomplete knowledge of the iron-chromium phase diagram at low temperatures and of the phenomena inducing preferential segregation of one element at grain boundaries or at surfaces. In this context, this work contributes to the multi-scale study of the model iron-chromium alloy and their free surfaces by numerical simulations. This study begins with ab initio calculations of properties related to the mixture of atoms of iron and chromium. We highlight complex dependency of the magnetic moments of the chromium atoms on their local chemical environment. Surface properties are also proving sensitive to magnetism. This is the case of impurity segregation of chromium in iron and of their interactions near the surface. In a second step, we construct a simple energy model for high numerical efficiency. It is based on pair interactions on a rigid lattice to which are given local chemical environment and temperature dependencies. With this model, we reproduce the ab initio results at zero temperature and experimental results at high temperature. We also deduce the solubility limits at all intermediate temperatures with mean field approximations that we compare to Monte Carlo simulations. The last step of our work is to introduce free surfaces in our model. We then study the effect of ab initio calculated bulk and surface properties on surface segregation.Finally, we calculate segregation isotherms. We therefore propose an evolution model of surface composition of iron-chromium alloys as a function of bulk composition. which are given local chemical environment and temperature dependencies. With this model, we reproduce the ab initio results at zero temperature and experimental results at high temperature. We also deduce the solubility limits at all intermediate temperatures with mean field approximations that

  6. Cavitation erosion of chromium-manganese and chromium-cobalt coatings processed by laser beam

    International Nuclear Information System (INIS)

    Giren, B.G.; Szkodo, M.

    2002-01-01

    In this work the cavitation erosion of chromium-manganese and chromium-cobalt clads were tested, each of them for three cases: (1) without additional processing; (2) after laser heating of the solid state and (3) after laser remelting of the material. Armco iron, carbon steel 45 and chromium-nickel steel 0H18N9T were used as substrates. C.W. CO 2 laser with a beam power of 1000 W was used as a source of radiation. The investigated samples were subjected to cavitation impingement in a rotating disk facility. The results indicate that laser processing of the thick, electrode deposited coatings by laser beam leads in some cases to an increase of their cavitation resistance. Strong dependence of the coatings performance on the substrate, both for the laser processed or unprocessed parts of the materials was also discovered. (author)

  7. Chromium Enrichment on P11 Ferritic Steel by Pack Cementation

    OpenAIRE

    Fauzi F. A.; Kurniawan T.; Salwani M. S.; Bin Y. S.; Harun W. S. W.

    2016-01-01

    The future thermal power plant is expected to operate at higher temperature to improve its efficiency and to reduce greenhouse gas emission. This target requires better corrosion properties of ferritic steels, which commonly used as materials for superheater and reheater of boiler tubes. In this work, chromium enrichment on the surface of ferritic steel is studied. The deposited chromium is expected to become a reservoir for the formation of chromia protective layer. Chromium was deposited on...

  8. Environmental exposure to arsenic and chromium in an industrial area

    OpenAIRE

    Vimercati, Luigi; Gatti, Maria F; Gagliardi, Tommaso; Cuccaro, Francesco; De Maria, Luigi; Caputi, Antonio; Quarato, Marco; Baldassarre, Antonio

    2017-01-01

    Arsenic and chromium are widespread environmental contaminants that affect global health due to their toxicity and carcinogenicity. To date, few studies have investigated exposure to arsenic and chromium in a population residing in a high-risk environmental area. The aim of this study is to evaluate the exposure to arsenic and chromium in the general population with no occupational exposure to these metals, resident in the industrial area of Taranto, Southern Italy, through biological monitor...

  9. Determination of tracer quantities of chromium in uranium

    International Nuclear Information System (INIS)

    Huart, A.

    1959-01-01

    A method is described for the photometric determination of chromium in uranium by absorbency at 540 mμ of the Cr(VI) diphenylcarbazide combination. After attack by nitric acid, the solution is made perchloric, and the chromium oxidised at the boiling point by permanganate. Excess oxidant is removed by hydrochloric acid. Study of operating conditions resulted in a method with an accuracy of ± 0,5 ppm for 0,5 to 15 ppm chromium in the metal. (author) [fr

  10. Analysis of molybdenum, chromium, vanadium and iron by polarographic techniques

    International Nuclear Information System (INIS)

    Al-Zand, T.K.

    1986-01-01

    The application of direct current Tast polarograph, differential pulse polarography and phase-selective alternative current Tast polarography to the problem of determining molybdenum, chromium, vanadium and iron in various supporting electrolytes is reported. The effect of the supporting electrolyte on the wave/peak potential and sensitivity of the metal ion have been examined. The polarographic methods were applied for simultaneous determination of chromium (3)/chromium (6), vanadium (4), vanadium (5) and iron (2)/iron (3) in different supporting electrolytes

  11. Multicomponent synthesis of unsymmetrical unsaturated N-heterocyclic carbene precursors and their related transition-metal complexes

    KAUST Repository

    Queval, Pierre; Jahier, Claire; Rouen, Mathieu; Artur, Isabelle; Legeay, Jean Christophe; Falivene, Laura; Toupet, Loï c J.; Cré visy, Christophe; Cavallo, Luigi; Baslé , Olivier; Mauduit, Marc

    2013-01-01

    A low-cost, modular, and easily scalable multicomponent procedure affording access in good yields and excellent selectivity (up to 93 %) to a wide range of (a)chiral unsymmetrical 1-aryl-3-cycloalkyl-imidazolium salts is disclosed. Electronic

  12. Dehydrogenative Synthesis of Carboxylic Acids from Primary Alcohols and Hydroxide Catalyzed by a Ruthenium N-Heterocyclic Carbene Complex

    DEFF Research Database (Denmark)

    Santilli, Carola; Makarov, Ilya; Fristrup, Peter

    2016-01-01

    reaction is most likely involved in this case. The kinetic isotope effect was determined to be 0.67 using 1-butanol as the substrate. A plausible catalytic cycle was characterized by DFT/B3LYP-D3 and involved coordination of the alcohol to the metal, β-hydride elimination, hydroxide attack...

  13. C-13 NMR Spectroscopy of N-Heterocyclic Carbenes Can Selectively Probe sigma Donation in Gold(I) Complexes

    NARCIS (Netherlands)

    Marchione, Demian; Izquierdo, Maria A.; Bistoni, Giovanni; Havenith, Remco W. A.; Macchioni, Alceo; Zuccaccia, Daniele; Tarantelli, Francesco; Belpassi, Leonardo

    The Dewar-Chatt-Duncanson (DCD) model provides a successful theoretical framework to describe the nature of the chemical bond in transition-metal compounds and is especially useful in structural chemistry and catalysis. However, how to actually measure its constituents (substrate- to-metal donation

  14. Mechanistic switch in dual gold catalysis of diynes: C(sp(3))-H activation through bifurcation--vinylidene versus carbene pathways.

    Science.gov (United States)

    Hansmann, Max M; Rudolph, Matthias; Rominger, Frank; Hashmi, A Stephen K

    2013-02-25

    The other side of the mountain: Changing the framework of diyne systems opens up new cyclization modes for dual gold catalysis. Instead of a 5-endo cyclization and gold vinylidenes a 6-endo cyclization gives rise to gold-stabilized carbenes as key intermediates for selective C-H insertions. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Rhodium-catalyzed NH insertion of pyridyl carbenes derived from pyridotriazoles: a general and efficient approach to 2-picolylamines and imidazo[1,5-a]pyridines.

    Science.gov (United States)

    Shi, Yi; Gulevich, Anton V; Gevorgyan, Vladimir

    2014-12-15

    A general and efficient NH insertion reaction of rhodium pyridyl carbenes derived from pyridotriazoles was developed. Various NH-containing compounds, including amides, anilines, enamines, and aliphatic amines, smoothly underwent the NH insertion reaction to afford 2-picolylamine derivatives. The developed transformation was further utilized in a facile one-pot synthesis of imidazo[1,5-a]pyridines. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Stabilization and solidification of chromium-contaminated soil

    Energy Technology Data Exchange (ETDEWEB)

    Cherne, C.A.; Thomson, B.M. [Univ. of New Mexico, Albuquerque, NM (United States). Civil Engineering Dept.; Conway, R. [Sandia National Labs., Albuquerque, NM (United States)

    1997-11-01

    Chromium-contaminated soil is a common environmental problem in the United States as a result of numerous industrial processes involving chromium. Hexavalent chromium [Cr(VI)] is the species of most concern because of its toxicity and mobility in groundwater. One method of diminishing the environmental impact of chromium is to reduce it to a trivalent oxidation state [Cr(III)], in which it is relatively insoluble and nontoxic. This study investigated a stabilization and solidification process to minimize the chromium concentration in the Toxicity Characteristic Leaching Procedure (TCLP) extract and to produce a solidified waste form with a compressive strength in the range of 150 to 300 pounds per square inch (psi). To minimize the chromium in the TCLP extract, the chromium had to be reduced to the trivalent oxidation state. The average used in this study was an alluvium contaminated with chromic and sulfuric acid solutions. The chromium concentration in the in the in situ soil was 1212 milligrams per kilogram (mg/kg) total chromium and 275 mg/kg Cr(VI). The effectiveness of iron, ferrous sulfate to reduce Cr(VI) was tested in batch experiments.

  17. Chromium depletion from stainless steels during vacuum annealing

    International Nuclear Information System (INIS)

    Smith, A.F.; Hales, R.

    1977-01-01

    During selective chromium oxidation of stainless steels the changes in chromium concentration at the metal surface and in the metal have an important bearing on the overall oxidation performance. It has been proposed that an analogue of chromium behaviour during selective oxidation is obtained from volatilisation of chromium during high temperature vacuum annealing. In the present report the evaporation of chromium from 316 type of steel, vacuum annealed at 1,000 0 C, has been investigated by means of energy dispersive X-ray analysis and by neutron activation analysis. It was established that chromium loss from austenitic stainless steels is rate controlled by interdiffusion in the alloy. As predicted the chromium concentration at the metal surface decreased with increasing vacuum annealing time. The chromium depletion profile in the metal was in good agreement with the previously derived model apart from an anomalous region near the surface. Here the higher resolution of the neutron activation technique indicated a zone within approximately 2μm of the surface where the chromium concentration decreased more steeply than expected. (orig.) [de

  18. Laboratory Automatic Titration of Chromium Plating and Electropolishing Solutions

    National Research Council Canada - National Science Library

    Sopok, Samuel

    2001-01-01

    .... The analytical chemistry literature lacks an adequate automatic titration method for the monitoring of chromic acid in chromium plating solutions and the monitoring of phosphoric and sulfuric acids...

  19. Stabilization and solidification of chromium-contaminated soil

    International Nuclear Information System (INIS)

    Cherne, C.A.; Thomson, B.M.

    1997-11-01

    Chromium-contaminated soil is a common environmental problem in the United States as a result of numerous industrial processes involving chromium. Hexavalent chromium [Cr(VI)] is the species of most concern because of its toxicity and mobility in groundwater. One method of diminishing the environmental impact of chromium is to reduce it to a trivalent oxidation state [Cr(III)], in which it is relatively insoluble and nontoxic. This study investigated a stabilization and solidification process to minimize the chromium concentration in the Toxicity Characteristic Leaching Procedure (TCLP) extract and to produce a solidified waste form with a compressive strength in the range of 150 to 300 pounds per square inch (psi). To minimize the chromium in the TCLP extract, the chromium had to be reduced to the trivalent oxidation state. The average used in this study was an alluvium contaminated with chromic and sulfuric acid solutions. The chromium concentration in the in the in situ soil was 1212 milligrams per kilogram (mg/kg) total chromium and 275 mg/kg Cr(VI). The effectiveness of iron, ferrous sulfate to reduce Cr(VI) was tested in batch experiments

  20. Oxygen Atom Transfer Using an Iron(IV)-Oxo Embedded in a Tetracyclic N-Heterocyclic Carbene System: How Does the Reactivity Compare to Cytochrome P450 Compound I?

    Science.gov (United States)

    Cantú Reinhard, Fabián G; de Visser, Sam P

    2017-02-24

    N-Heterocyclic carbenes (NHC) are commonly featured as ligands in transition metal catalysis. Recently, a cyclic system containing four NHC groups with a central iron atom was synthesized and its iron(IV)-oxo species, [Fe IV (O)(cNHC 4 )] 2+ , was characterized. This tetracyclic NHC ligand system may give the iron(IV)-oxo species unique catalytic properties as compared to traditional non-heme and heme iron ligand systems. Therefore, we performed a computational study on the structure and reactivity of the [Fe IV (O)(cNHC 4 )] 2+ complex in substrate hydroxylation and epoxidation reactions. The reactivity patterns are compared with cytochrome P450 Compound I and non-heme iron(IV)-oxo models and it is shown that the [Fe IV (O)(cNHC 4 )] 2+ system is an effective oxidant with oxidative power analogous to P450 Compound I. Unfortunately, in polar solvents, a solvent molecule will bind to the sixth ligand position and decrease the catalytic activity of the oxidant. A molecular orbital and valence bond analysis provides insight into the origin of the reactivity differences and makes predictions of how to further exploit these systems in chemical catalysis. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Uranium metalla-allenes with carbene imido R_2C=U"I"V=NR' units (R=Ph_2PNSiMe_3; R'=CPh_3): alkali-metal-mediated push-pull effects with an amido auxiliary

    International Nuclear Information System (INIS)

    Lu, Erli; Tuna, Floriana; Kaltsoyannis, Nikolas; Liddle, Stephen T.; Lewis, William

    2016-01-01

    We report uranium(IV)-carbene-imido-amide metalla-allene complexes [U(BIPM"T"M"S)(NCPh_3)(NHCPh_3)(M)] (BIPM"T"M"S=C(PPh_2NSiMe_3)_2; M=Li or K) that can be described as R_2C=U=NR' push-pull metalla-allene units, as organometallic counterparts of the well-known push-pull organic allenes. The solid-state structures reveal that the R_2C=U=NR' units adopt highly unusual cis-arrangements, which are also reproduced by gas-phase theoretical studies conducted without the alkali metals to remove their potential structure-directing roles. Computational studies confirm the double-bond nature of the U=NR' and U=CR_2 interactions, the latter increasingly attenuated by potassium then lithium when compared to the hypothetical alkali-metal-free anion. Combined experimental and theoretical data show that the push-pull effect induced by the alkali metal cations and amide auxiliary gives a fundamental and tunable structural influence over the C=U"I"V=N units. (copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  2. Specification for corrosion-resisting chromium and chromium-nickel steel bare and composite metal cored and stranded arc welding electrodes and welding rods

    International Nuclear Information System (INIS)

    Anon.

    1983-01-01

    This specification prescribes requirements for corrosion or heat resisting chromium and chromium-nickel steel electrodes and welding rods. These electrodes and welding rods are normally used for arc welding and include those alloy steels designated as corrosion or heat-resisting chromium and chromium-nickel steels, in which chromium exceeds 4.0 percent and nickel does not exceed 50.0 percent

  3. Voltammetric study of chromium(VI)-ammonia/ammonium chloride solutions in the presence of dimethylglyoxime

    International Nuclear Information System (INIS)

    Ginzburg, V.G.; Salikhdzhanova, R.M.F.

    1987-01-01

    The authors believed complexation to be possible in the system Cr(VI)-dimethylglyoxime (DMG, H 2 D) by reduction of Cr(VI) to Cr(III) on a mercury electrode. The DMG can be used in chromium voltammetry and is promising for a number of reasons: The Cr(III) has an affinity for donor nitrogen atoms in the DMG molecule. Insertion of the H 2 D into the inner sphere of the complex is expected to weaken the bond between the Cr(III) and the hydroxyl group, slow down formation of the insoluble hydroxide Cr(OH) 3 , and lower the rate of the electrode reaction Cr(III) → Cr(II). Molecules of H 2 D adsorb on a mercury electrode. It is therefore possible to accelerate the electrode process by including adsorptive preconcentration of the chromium and thus lowering its detection limit. This paper reports the voltammetric behavior of the system Cr(VI)-DMG-NH 4 + (proton donor) for the purpose of lowering the chromium detection limit

  4. Determination of iron, nickel, and chromium in the Masurca simulation rods

    International Nuclear Information System (INIS)

    Brigaudeau, M.; Pierdet, S.

    1969-01-01

    A method has been developed for determining the iron, nickel and chromium content of sintered ternary oxide rods designed to simulate structural elements in the reactor Masurca. During this work a calculation was made of the conditional constant of the Fe-EDTA complex in a formic buffer solution, and of that, of the Ni-EDTA complex in an ammoniacal buffer. From these two values it appears that it is not possible to carry out the iron and nickel determinations with a standard EDTA solution when these two elements are present simultaneously. That is the reason for which, in this case, a separation of the Fe and Ni is carried out in 8 N HCl solution on an anion exchange resin. Each element is then dosed by titricolorimetry. Chromium is determined by the same technique without prior separation. The reproducibility of the method has been calculated for each of the three elements. The relative accuracy is: 0.58 per cent for the iron; 1.41 per cent for the nickel; 0.39 per cent for the chromium. (authors) [fr

  5. The nature of the U=C double bond: pushing the stability of high-oxidation-state uranium carbenes to the limit

    Energy Technology Data Exchange (ETDEWEB)

    Cooper, Oliver J.; Mills, David P.; McMaster, Jonathan; Lewis, William; Blake, Alexander J.; Liddle, Stephen T. [School of Chemistry, University of Nottingham (United Kingdom); Tuna, Floriana; McInnes, Eric J.L. [EPSRC National UK EPR Facility, School of Chemistry and Photon Science Institute, The University of Manchester (United Kingdom)

    2013-05-27

    Treatment of [K(BIPM{sup Mes}H)] (BIPM{sup Mes}={C(PPh_2NMes)_2}{sup 2-}; Mes=C{sub 6}H{sub 2}-2,4,6-Me{sub 3}) with [UCl{sub 4}(thf){sub 3}] (1 equiv) afforded [U(BIPM{sup Mes}H)(Cl){sub 3}(thf)] (1), which generated [U(BIPM{sup Mes})(Cl){sub 2}(thf){sub 2}] (2), following treatment with benzyl potassium. Attempts to oxidise 2 resulted in intractable mixtures, ligand scrambling to give [U(BIPM{sup Mes}){sub 2}] or the formation of [U(BIPM{sup Mes}H)(O){sub 2}(Cl)(thf)] (3). The complex [U(BIPM{sup Dipp})(μ-Cl){sub 4}(Li){sub 2}(OEt{sub 2})(tmeda)] (4) (BIPM{sup Dipp}={C(PPh_2NDipp)_2}{sup 2-}; Dipp=C{sub 6}H{sub 3}-2,6-iPr{sub 2}; tmeda=N,N,N',N'-tetramethylethylenediamine) was prepared from [Li{sub 2}(BIPM{sup Dipp})(tmeda)] and [UCl{sub 4}(thf){sub 3}] and, following reflux in toluene, could be isolated as [U(BIPM{sup Dipp})(Cl){sub 2}(thf){sub 2}] (5). Treatment of 4 with iodine (0.5 equiv) afforded [U(BIPM{sup Dipp})(Cl){sub 2}(μ-Cl){sub 2}(Li)(thf){sub 2}] (6). Complex 6 resists oxidation, and treating 4 or 5 with N-oxides gives [U(BIPM {sup Dipp}H)(O){sub 2}-(μ-Cl){sub 2}Li(tmeda)] (7) and [{U(BIPM"D"i"p"pH)(O)_2(μ-Cl)}{sub 2}] (8). Treatment of 4 with tBuOLi (3 equiv) and I{sub 2} (1 equiv) gives [U(BIPM{sup Dipp})(OtBu){sub 3}(I)] (9), which represents an exceptionally rare example of a crystallographically authenticated uranium(VI)-carbon σ bond. Although 9 appears sterically saturated, it decomposes over time to give [U(BIPM{sup Dipp})(OtBu){sub 3}]. Complex 4 reacts with PhCOtBu and Ph{sub 2}CO to form [U(BIPM{sup Dipp})(μ-Cl){sub 4}(Li){sub 2}(tmeda)(OCPhtBu)] (10) and [U(BIPM{sup Dipp})(Cl)(μ-Cl){sub 2}(Li)(tmeda)(OCPh{sub 2})] (11). In contrast, complex 5 does not react with PhCOtBu and Ph{sub 2}CO, which we attribute to steric blocking. However, complexes 5 and 6 react with PhCHO to afford (DippNPPh{sub 2}){sub 2}C=C(H)Ph (12). Complex 9 does not react with PhCOtBu, Ph{sub 2}CO or PhCHO; this is attributed to steric blocking

  6. Structured mirror array for two-dimensional collimation of a chromium beam in atom lithography

    International Nuclear Information System (INIS)

    Zhang Wan-Jing; Ma Yan; Li Tong-Bao; Zhang Ping-Ping; Deng Xiao; Chen Sheng; Xiao Sheng-Wei

    2013-01-01

    Direct-write atom lithography, one of the potential nanofabrication techniques, is restricted by some difficulties in producing optical masks for the deposition of complex structures. In order to make further progress, a structured mirror array is developed to transversely collimate the chromium atomic beam in two dimensions. The best collimation is obtained when the laser red detunes by natural line-width of transition 7 S 3 → 7 P 0 4 of the chromium atom. The collimation ratio is 0.45 vertically (in x axis), and it is 0.55 horizontally (in y axis). The theoretical model is also simulated, and success of our structured mirror array is achieved. (atomic and molecular physics)

  7. Wet skins tanning with chromium in dense CO{sub 2} under pressure; Tannage au chrome de peaux humides en CO{sub 2} dense sous pression

    Energy Technology Data Exchange (ETDEWEB)

    Saldinari, L. [Tanneries Roux SA, 26 - Romans Sur Isere (France)]|[Tanneries du Puy (France)]|[Tanneries d' Annonay, 07 (France); Dutel, Ch. [Societe ATC (France); Perre, Ch. [CEA Centre de Pierrelatte (DCC/DTE/SLC), 26 (France)

    2000-07-01

    An ancestral gesture steadily improved through the centuries, the transformation of skins into leather includes several stages of which the principal one is tanning. Today, 90 % of the world's leather products are tanned with chromium. However, this stage is an environmental liability, and reducing the volume and chromium content of the waste has become a major issue. A first study on skin degreasing by dense CO{sub 2} helped sharply reduce the volume of the fatty effluents. To replace water by dense CO{sub 2} as the tanning medium was the logical next step. The present study was carried out in cooperation with three tanneries in the Rhone-Alpes-Auvergne area of France and a manufacturer of tanning materials. The difficulty of the study was the chemically opposed character of the two media involved. CO{sub 2} is a non-polar and lipophilic solvent while inorganic chromium is insoluble. The water present in the treated skin is a polar and ionic reaction medium and one of the reagents in tanning chemistry. The mixture of these two partially miscible compounds gives a pH 3 by carbonic acid formation. Tanning is based on the reactivity of collagen, the main component of the skin, with hydroxylated complexes of chromium. Collagen is a protein containing some chemical functions, amines (R-NH{sub 2}) and carboxylic (R-COOH) for example. These functions impart an amphoteric character to the compound. The WERNER theory of complex salts explains the formation of hydroxylated complexes of chromium and their fixing on the carboxylic functions of collagen by oxolation. pH is the key parameter in tanning. The success of the process demands chromium impregnation without fixing it at a pH lower than 5, and then to fix it by increasing the pH. This opened two alternatives for transferring chromium in the skin: solubilize chromium in CO{sub 2} via soluble organometallic complexes; or put the chromium salt into suspension without solubilizing it. The best results were obtained

  8. Ultra low nanowear in novel chromium/amorphous chromium carbide nanocomposite films

    Science.gov (United States)

    Yate, Luis; Martínez-de-Olcoz, Leyre; Esteve, Joan; Lousa, Arturo

    2017-10-01

    In this work, we report the first observation of novel nanocomposite thin films consisting of nanocrystalline chromium embedded in an amorphous chromium carbide matrix (nc-Cr/a-CrC) with relatively high hardness (∼22,3 GPa) and ultra low nanowear. The films were deposited onto silicon substrates using a magnetic filtered cathodic arc deposition system at various negative bias voltages, from 50 to 450 V. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) suggested the co-existence of chromium and chromium carbide phases, while high resolution transmission electron microscopy (HRTEM) confirmed the presence of the nc-Cr/a-CrC structure. The friction coefficient measured with the ball-on disk technique and the nanowear results showed a strong correlation between the macro and nano-tribological properties of the samples. These novel nanocomposite films show promising properties as solid lubricant and wear resistant coatings with relatively high hardness, low friction coefficient and ultra low nanowear.

  9. COST EFFECTIVE CONTROL OF HEXAVALENT CHROMIUM AIR EMISSIONS FROM FUNCTIONAL CHROMIUM ELECTROPLATING

    Science.gov (United States)

    This paper will summrize thie pollution prevention (p2) method to control stack emissions from hard chromium plating operations performed by the USEPA's National Risk Management Research Laboratory (NRMRL) over the last four years. During literature research and user surveys, it...

  10. ALUMINUM AND CHROMIUM LEACHING WORKSHOP WHITEPAPER

    International Nuclear Information System (INIS)

    McCabe, D; Jeff Pike, J; Bill Wilmarth, B

    2007-01-01

    A workshop was held on January 23-24, 2007 to discuss the status of processes to leach constituents from High Level Waste (HLW) sludges at the Hanford and Savannah River Sites. The objective of the workshop was to examine the needs and requirements for the HLW flowsheet for each site, discuss the status of knowledge of the leaching processes, communicate the research plans, and identify opportunities for synergy to address knowledge gaps. The purpose of leaching of non-radioactive constituents from the sludge waste is to reduce the burden of material that must be vitrified in the HLW melter systems, resulting in reduced HLW glass waste volume, reduced disposal costs, shorter process schedules, and higher facility throughput rates. The leaching process is estimated to reduce the operating life cycle of SRS by seven years and decrease the number of HLW canisters to be disposed in the Repository by 1000 [Gillam et al., 2006]. Comparably at Hanford, the aluminum and chromium leaching processes are estimated to reduce the operating life cycle of the Waste Treatment Plant by 20 years and decrease the number of canisters to the Repository by 15,000-30,000 [Gilbert, 2007]. These leaching processes will save the Department of Energy (DOE) billions of dollars in clean up and disposal costs. The primary constituents targeted for removal by leaching are aluminum and chromium. It is desirable to have some aluminum in glass to improve its durability; however, too much aluminum can increase the sludge viscosity, glass viscosity, and reduce overall process throughput. Chromium leaching is necessary to prevent formation of crystalline compounds in the glass, but is only needed at Hanford because of differences in the sludge waste chemistry at the two sites. Improving glass formulations to increase tolerance of aluminum and chromium is another approach to decrease HLW glass volume. It is likely that an optimum condition can be found by both performing leaching and improving

  11. Chromium in urothelial carcinoma of the bladder.

    Science.gov (United States)

    Golabek, Tomasz; Socha, Katarzyna; Kudelski, Jacek; Darewicz, Barbara; Markiewicz-Zukowska, Renata; Chlosta, Piotr; Borawska, Maria

    2017-12-23

    Many epidemiological and experimental studies report a strong role of chemical carcinogens in the etiology of bladder cancer. However, the involvement of heavy metals in tumourigenesis of urothelial carcinoma of the bladder has been poorly investigated. Therefore, the aim of this study was to examine the relationship between chromium (Cr) and bladder cancer. Chromium concentration in two 36-sample series of bladder cancer tissue and sera from patients with this neoplasm were matched with those of a control group. The amount of trace elements in every tissue sample was determined using atomic absorption spectrometry. This was correlated with tumour stage. While the median chromium concentration levels reached statistically higher values in the bladder cancer tissue, compared with the non-cancer tissue (99.632ng/g and 33.144ng/g, respectively; p<0.001), the median Cr levels in the sera of the patients with this carcinoma showed no statistical difference when compared to those of the control group (0.511μg/l and 0.710μg/l, respectively; p=0.408). The median levels of Cr in the bladder tissue, depending on the stage of the tumour, compared with the tissue without the neoplasm, observed the same relationship for both non-muscle invasive and muscle-invasive tumours (p<0.001 and p<0.01, respectively). This study shows that patients with urothelial carcinoma of the bladder had higher tissue Cr levels than people without tumour, while no difference was found in the Cr serum levels between the two groups of patients under investigation.

  12. Dephosphorization of melts with chromium content

    International Nuclear Information System (INIS)

    Motloch, Z.

    1985-01-01

    A survey is given of the results of laboratory and pilot plant research into the dephosphorization of high-chromium melts reported in the literature, mostly Japanese. The use of high-alloy chromium and chromium-nickel steels in nuclear power engineering showed the negative impact of phosphorus on stress corrosion at high temperatures and on the development of cracks under overlays during welding. For a number of years attention is therefore being devoted to the attainment of a low phosphorus content in these steels. Current dephosphorization methods may be divided into oxidation and reduction methods. Oxidation dephosphorization may be carried out using synthetic mixtures: in the use of CaO-FeCl 2 , BaO-BaCl 2 -Cr 2 O 3 , Li 2 CO 3 -CaO-CaF 2 -FeO and Na 2 CO 3 /K 2 CO 3 -NaCl/KCl/KF/CaCl 2 /FeCl 2 a high initial C content, low content of Cr and Si and a low temperature of the melt are advantageous for dephosphorization. Experiments have also been made with dephosphorization in a bottom-blown oxygen converter and in an AOD converter. The most frequently used substances for reduction dephosphorization are calcium and calcium carbide; the best C content ranges between 0.5 and 1.8%, a high Cr content and a high bath temperature are also advantageous. The use of the reduction procedure is greatly limited by the generation of highly toxic phosphine. Another tested method - electroslag remelting is not suitable for commercial application for its economic exactingness. (A.K.)

  13. Ultracold chromium: a dipolar quantum gas

    International Nuclear Information System (INIS)

    Pfau, T.; Stuhler, J.; Griesmaier, A.; Fattori, M.; Koch, T.

    2005-01-01

    We report on our recent achievement of a Bose-Einstein condensate in a gas of chromium atoms. Peculiar electronic and magnetic properties of chromium require the implementation of novel cooling strategies. We observe up to ∼ 10 5 condensed 52 Cr atoms after forced evaporation within a crossed optical dipole trap. Due to its large magnetic moment (6μ B ), the dipole-dipole interaction strength in chromium is comparable with the one of the van der Waals interaction. We prove the anisotropic nature of the dipolar interaction by releasing the condensate from a cigar shaped trap and observe, in time of flight measurements, the change of the aspect-ratio for different in-trap orientations of the atomic dipoles. We also report on the recent observation of 14 Feshbach resonances in elastic collisions between polarized ultra-cold 52 Cr atoms. This is the first Ballistic expansion of a dipolar quantum gas: The anisotropic interaction leads to a different expansion dynamics for the case of the magnetic dipoles aligned with the symmetry axis of the cigar shaped trap as compared with the dipoles oriented perpendicular to the axis of the cigar. The straight lines correspond to the theoretical expectation according to mean field theory without free parameters. observation of collisional Feshbach resonances in an atomic species with more than one valence electron. Moreover, such resonances constitute an important tool towards the realization of a purely dipolar interacting gas because they can be used to change strength and sign of the van der Waals interaction. (author)

  14. Predicting chromium (VI) adsorption rate in the treatment of liquid ...

    African Journals Online (AJOL)

    Administrator

    The adsorption rate of chromium (VI) on commercial activated carbon during the ... time and initial chromium (VI) ion concentration. .... model, the separation factor r, according to Calvo et al (2001) cited .... Lead (II) and nickel (II) adsorption kinetics .... heavy metal by Talaromyces helicus: a trained fungus for copper and.

  15. Bioremediation of chromium in tannery effluent by microbial consortia

    African Journals Online (AJOL)

    Chromium is the most toxic and common among the heavy metal pollutants of industrial effluents. In the present work the chromium remediation ability of Bacillus subtilis, Pseudomonas aeruginosa and Saccharomyces cerevisiae in consortia and in their immobilized forms was studied and their efficiencies were compared.

  16. The commensurate spin excitation in chromium: A polarised neutron investigation

    International Nuclear Information System (INIS)

    Pynn, R.; Stirling, W.G.

    1991-01-01

    A polarised neutron experiment with neutron energy analysis has been performed with a single-Q sample of chromium in a large magnetic field. The 4-meV ''commensurate'' mode is found to involve spin fluctuations parallel to the ordered chromium moments. 8 refs., 3 figs

  17. 76 FR 8773 - Superalloy Degassed Chromium From Japan

    Science.gov (United States)

    2011-02-15

    ... INTERNATIONAL TRADE COMMISSION [Investigation No. 731-TA-1090 (Review)] Superalloy Degassed Chromium From Japan AGENCY: United States International Trade Commission. ACTION: Termination of five-year... revocation of the antidumping duty order on superalloy degassed chromium from Japan would be likely to lead...

  18. Predicting chromium (VI) adsorption rate in the treatment of liquid ...

    African Journals Online (AJOL)

    The adsorption rate of chromium (VI) on commercial activated carbon during the treatment of the flocculation effluent of liquid-phase oil-based drill-cuttings has been investigated in terms of contact time and initial chromium (VI) ion concentration. Homogenizing 1 g of the activated carbon with 100 ml of the flocculation ...

  19. Biosorption of chromium by mangrove-derived Aplanochytrium sp ...

    African Journals Online (AJOL)

    The microbial dried biomass of Thraustochytrids is used as bioadsorbent for the removal of the chromium in aqueous solution. In this investigation, three species of Thraustochydrids namely Aplanochytrium sp., Thraustochytrium sp. and Schizochytrium sp. were tested for the efficiency of chromium accumulation by culturing ...

  20. Optimization of chromium biosorption in aqueous solution by marine ...

    African Journals Online (AJOL)

    Optimization of a chromium biosorption process was performed by varying three independent variables pH (0.5 to 3.5), initial chromium ion concentration (10 to 30 mg/L), and Yarrowia lipolytica dosage (2 to 4 g/L) using a Doehlert experimental design (DD) involving response surface methodology (RSM). For the maximum ...