WorldWideScience

Sample records for illegaalne reiv kalinini

  1. Kunst elab Kalinini tehases

    Index Scriptorium Estoniae

    2002-01-01

    Šveitsi ja prantsuse kunstnike Delphine Reisti, Laurent Fauloni ja Sebastien Perroud' installatsioonide näitus "For Songs for Siivi" endises Kalinini tehases Tallinnas. Näitusega kaasnevad viiuldaja Mathieu Werchowski kontserdid. Squat art on kunst, mis tekib ühisolemise produktina ja jääb tegevuskohta näitamiseks

  2. Kalinini tehas hõivatud

    Index Scriptorium Estoniae

    2002-01-01

    Prantsuse kunstnike Delphine Reisti, Laurent Fauloni, Sebastien Perroud' ja viiuldaja Mathieu Werchowsky ühisnäitus "Four songs for Siivi" Tallinna endises Kalinini tehases. Kunstnikud esitlevad igaüks üht installatsiooni, M. Werchowsky annab mitu kontserti

  3. Enhancing the magnetic coupling of oxalato-bridged Re(IV)2M(II) (M=Mn, Co, Ni, and Cu) trinuclear complexes via peripheral halide ligand effects.

    Science.gov (United States)

    Martínez-Lillo, José; Mastropietro, Teresa F; De Munno, Giovanni; Lloret, Francesc; Julve, Miguel; Faus, Juan

    2011-06-20

    Four heterotrinuclear Re(IV)(2)M(II) compounds of general formula (NBu(4))(2)[{Re(IV)Br(4)(μ-ox)}(2)M(II)(Him)(2)] [NBu(4)(+) = tetra-n-butylammonium cation, ox = oxalate, Him = imidazole; M = Mn (1), Co (2), Ni (3), and Cu (4)] have been synthesized by using the novel mononuclear complex [Re(IV)Br(4)(ox)](2-) as a ligand toward divalent first-row transition metal ions in the presence of imidazole. Compounds 1-4 are isostructural complexes whose structure contains discrete trinuclear [{Re(IV)Br(4)(μ-ox)}(2)M(II)(Him)(2)](2-) anions and bulky NBu(4)(+) cations. The Re and M atoms are six-coordinated: four peripheral bromo and two oxalate-oxygens (at Re), and two cis-coordinated imidazole molecules and four oxygen atoms from two oxalate ligands (at M), build distorted octahedral surroundings. Two peripheral [ReBr(4)(ox)](2-) units act as bidentate ligands through the oxalate group toward the central [M(II)(Him)(2)] fragment affording the trinuclear entities. The values of the intramolecular Re···M separation are 5.62(1) (1), 5.51(1) (2), 5.46(1) (3), and 5.55(1) Å (4). Magnetic susceptibility measurements on polycrystalline samples of 1-4 in the temperature range of 1.9-300 K show the occurrence of intramolecular antiferro- [J = -1.1 cm(-1) (1)] and ferromagnetic interactions [J = +3.9 (2), +19.7 (3), and +14.4 cm(-1) (4)], the Hamiltonian being defined as Ĥ = -J [Ŝ(M)(Ŝ(Re1) + Ŝ(Re2))]. The larger spin delocalization on the oxalato bridge in 1-4 when compared to the trinuclear Re(IV)(2)M(II) complexes with chloro instead of bromo as peripheral ligands (1'-4') accounts for the strengthening of the magnetic interactions in 1-4 [J = -0.35 (1'), +14.2 (3'), and +7.7 cm(-1) (4')]. An incipient frequency dependence of the out-of-phase ac signals of 3 at very low temperatures is reminiscent of a system with slow relaxation of the magnetization, a phenomenon characteristic of single-molecule magnet behavior.

  4. Illegaalne relvaäri on kui ämblikuvõrk / Toomas Sildam, Toomas Mattson

    Index Scriptorium Estoniae

    Sildam, Toomas, 1961-

    1995-01-01

    Venemaa süüdistused. Kaitseliit. Politsei. Ilmunud ka: Vetshernije Vesti, 13. nov. 1995, lk. 1; 14. nov. 1995, lk. 5; 16. nov. 1995, lk. 5; 18. nov. 1995, lk. 7; Pühapäevaleht, 11. nov. 1995, lk. 10-12; Molodjozh Estonii : Kupetsheskaja Gavan, 17. nov. 1995, lk. 8-9

  5. Prantsuse kunstnikud asustasid vana tehase / Johannes Saar

    Index Scriptorium Estoniae

    Saar, Johannes, 1965-

    2002-01-01

    Prantsuse kunstnike (Delphine Reist, Laurent Faulon, Sebastien Perroud) ja viiuldaja Mathieu Werchowsky Tallinnas valminud installatsiooninäitus "Neli laulu Siivile" vanas Kalinini tehasehoones 7.-12. juunini

  6. 1.1.3. Substitution on Re(IV complexes: a tool for the synthesis of novel mono- and polynuclear compounds

    Directory of Open Access Journals (Sweden)

    Carlos Kremer

    2014-04-01

    Full Text Available Rhenium(IV complexes are relatively scarce if compared with those of other oxidation states as Re(V or Re(VII. It is a 5d3 ion, and usually forms octahedral complexes which are reasonably stable against redox processes and inert to ligand substitution. This is the basis for the preparation of mononuclear species that can act as ligands towards other transition metal ions. For example, complexes containing dicarboxylic ligands, [ReX4(ox]2–and [ReX4(mal]2– (X = Cl, Br; ox = oxalato; mal = malonato, or N-donor ligands, [ReCl5(pyz]– (pyz = pyrazine have been used as building blocks to construct heteropolynuclear complexes. The different synthetic routes, as well as the designed structures, from discrete binuclear complexes to extended chain-like compounds, are reviewed in this contribution.

  7. Synthesis of a ‘4+1’ Re(V complex from Re(III, and its disproportionation to Re(IV and Re(VII

    Directory of Open Access Journals (Sweden)

    P. Mayer

    2010-06-01

    Full Text Available The distorted octahedral oxorhenium(V complex [ReOCl(had] (1 (H2had = N,N-bis(2-hydroxybenzyl-2-(2-aminoethyldimethylamine was prepared from the oxidation of [ReCl3 (MeCN(PPh32] by dioxygen in the presence of H2 had in ethanol. This reaction was done under reflux conditions for a relatively short reaction time of an hour. However, increasing the reaction period to seven days led to the disproportionation of 1 to [ReIVCl(had(PPh3](Re sup>VIIO4 (2. Both compounds were characterized by infra-red spectroscopy and X-ray crystallography.

  8. Kükitajate kunst ja kõrvalhoidmise strateegiad = Squat-art and strategies of choosing the edge / Karin Laansoo

    Index Scriptorium Estoniae

    Laansoo, Karin, 1976-

    2002-01-01

    Prantsuse kunstnikud Delphine Reist, Laurent Faulon, Sebastien Perroud ja Mathiue Werchowsky tegid Tallinnas Kalinini tehasehoones squart'näituse "Neli laulu Siivile". Kuraator Andres Lõo.Four songs for Siivi, kunstinäitus (2002 : Tallinn)

  9. Ekspansioon / Alina Kurvitz

    Index Scriptorium Estoniae

    Kurvitz, Alina

    2002-01-01

    Prantsuse kunstnike Delphine Reisti, Laurent Fauloni ja Sebastien Perroud' installatsioonide näitus "Four songs for Siivi" Tallinnas mahajäetud Kalinini tehases. Näitusega kaasnevad viiuldaja Mathieu Werchowsky kontserdid

  10. Obrazõ Putina : kak jego vidjat hudozhniki / Kerstin Holm

    Index Scriptorium Estoniae

    Holm, Kerstin

    2005-01-01

    Venemaa presidenti Vladimir Putinit kujutavatest taiestest. Kunstnike Andrei Loginovi, Nikas Safronovi, Zurab Tsereteli, Sergei Kalinini ja Farid Bogdanovi, rühmituse "Sinije nosõ" ning David Ter-Oganjani töödest

  11. Kükitajate kunst ja kõrvalhoidmise strateegiad = Squat-art and strategies of choosing the edge / Karin Laansoo

    Index Scriptorium Estoniae

    Laansoo, Karin, 1976-

    2002-01-01

    Prantsuse kunstnikud Delphine Reist, Laurent Faulon, Sebastien Perroud ja Mathiue Werchowsky tegid Tallinnas Kalinini tehasehoones squart'näituse "Neli laulu Siivile". Kuraator Andres Lõo.Four songs for Siivi, kunstinäitus (2002 : Tallinn)

  12. One-dimensional coordination polymers of [Co3(dpa)4]2+ and [MF6]2- (M = ReIV, ZrIV and SnIV)

    DEFF Research Database (Denmark)

    Bulicanu, Vladimir; Pedersen, Kasper Steen; Rouzières, Mathieu;

    2015-01-01

    One-dimensional coordination polymers of alternating metal-metal bonded trinuclear [Co3(dpa)4]2+ (dpa = the anion of 2,2'-dipyridylamine) building blocks and [ReF6]2- (1), [ZrF6]2- (2) or [SnF6]2- (3) linkers have been self-assembled and crystallographically characterized. Magnetic measurements...

  13. Heterotetranuclear oxalato-bridged Re(IV)3M(II) (M = Mn, Fe, Co, Ni, Cu) complexes: a new example of a single-molecule magnet (M = Ni).

    Science.gov (United States)

    Martínez-Lillo, José; Armentano, Donatella; De Munno, Giovanni; Wernsdorfer, Wolfgang; Clemente-Juan, Juan Modesto; Krzystek, J; Lloret, Francesc; Julve, Miguel; Faus, Juan

    2009-04-01

    The use of the mononuclear species (NBu(4))(2)[Re(IV)Cl(4)(ox)] (NBu(4)(+) = tetra-n-butylammonium cation; ox = oxalate dianion) as a ligand toward fully solvated divalent first-row transition-metal ions affords the tetranuclear complexes (NBu(4))(4)[{Re(IV)Cl(4)(mu-ox)}(3)M(II)] with M = Mn (1), Fe (2), Co (3), Ni (4), and Cu (5). Their structure is made up of discrete [{ReCl(4)(mu-ox)}(3)M](4-) anions and bulky NBu(4)(+) cations. The complexes 2-5 crystallize in the triclinic system with space group P1; 2 and 5 as well as 3 and 4 are isostructural. The Re and M atoms exhibit somewhat distorted ReCl(4)O(2) and MO(6) octahedral surroundings, with the oxalate groups adopting the bis-bidentate bridging mode. Magnetic susceptibility measurements on polycrystalline samples of 1-5 in the temperature range 1.9-300 K show the occurrence of intramolecular antiferromagnetic [J = -1.30 cm(-1) (1)] and ferromagnetic couplings [J = +1.62 (2), +3.0 (3), +16.3 (4), and +4.64 cm(-1) (5)], with the Hamiltonian being defined as H = -J[S(M)(S(Re1) + S(Re2) + S(Re3))]. Compound 4 is the first example of an oxalato-bridged heterometallic species that behaves as a single-molecule magnet with a ground-state spin S = (11)/(2) and D = -0.8(1) cm(-1), as shown by the study of its static and dynamic magnetic properties and a high-frequency electron paramagnetic resonance study on polycrystalline samples together with detailed micro-SQUID measurements on single crystals.

  14. Skandaalid : Eesti elu deodorant / Argo Ideon, Toomas Sildam

    Index Scriptorium Estoniae

    Ideon, Argo, 1966-

    1999-01-01

    Lisa: intervjuu Daniel Vaarikuga. 8 valitud skandaali, mis vapustasid Eestit: Tartu Kommertspanga pankrot. Rublamüük. Illegaalne relvaäri. Lindiskandaal. 10 milj. dollari kadumine. Tallinna Panga ja Ühispanga konflikt. Daiwa laen. Viinaga valijate häälte ostmine

  15. 108aastase Liviko tooted koguvad tunnustust nii kodus kui välismaal / Tiit Reinart

    Index Scriptorium Estoniae

    Reinart, Tiit, 1964-

    2006-01-01

    Tänavu tunnustati AS-i Liviko tooteid Vana Tallinna Liköör, Üx Vodka ja Vana Tallinn Cream ühel mainekamal rahvusvahelisel konkursil International Wine & Spirit Competition (IWSC), ühtlasi tegeleb ettevõte jätkuvalt tootearenduse ja kvaliteetveinide importimisega. Vt. samas: Maksumärgita alkohol on illegaalne

  16. São Paulo majad kõnelevad salakeeles / Filipp Kruusvall

    Index Scriptorium Estoniae

    Kruusvall, Filipp

    2015-01-01

    Artikkel tutvustab São Paulo tänavakunstnikke pixadoreseid, kes ronivad kõrghoonetele joonistama oma märguannet sotsiaalsest elususest. See illegaalne tegevus on ühtaegu hääl, sõnum kui ka karje ebaõigluse vastu ühes maailma ebaühtlasema varalise kihistumisega riigis Brasiilias

  17. São Paulo majad kõnelevad salakeeles / Filipp Kruusvall

    Index Scriptorium Estoniae

    Kruusvall, Filipp

    2015-01-01

    Artikkel tutvustab São Paulo tänavakunstnikke pixadoreseid, kes ronivad kõrghoonetele joonistama oma märguannet sotsiaalsest elususest. See illegaalne tegevus on ühtaegu hääl, sõnum kui ka karje ebaõigluse vastu ühes maailma ebaühtlasema varalise kihistumisega riigis Brasiilias

  18. Skandaalid : Eesti elu deodorant / Argo Ideon, Toomas Sildam

    Index Scriptorium Estoniae

    Ideon, Argo, 1966-

    1999-01-01

    Lisa: intervjuu Daniel Vaarikuga. 8 valitud skandaali, mis vapustasid Eestit: Tartu Kommertspanga pankrot. Rublamüük. Illegaalne relvaäri. Lindiskandaal. 10 milj. dollari kadumine. Tallinna Panga ja Ühispanga konflikt. Daiwa laen. Viinaga valijate häälte ostmine

  19. 108aastase Liviko tooted koguvad tunnustust nii kodus kui välismaal / Tiit Reinart

    Index Scriptorium Estoniae

    Reinart, Tiit, 1964-

    2006-01-01

    Tänavu tunnustati AS-i Liviko tooteid Vana Tallinna Liköör, Üx Vodka ja Vana Tallinn Cream ühel mainekamal rahvusvahelisel konkursil International Wine & Spirit Competition (IWSC), ühtlasi tegeleb ettevõte jätkuvalt tootearenduse ja kvaliteetveinide importimisega. Vt. samas: Maksumärgita alkohol on illegaalne

  20. Kus tondid Tallinnas pidu peavad?

    Index Scriptorium Estoniae

    2008-01-01

    Lagunevatest hoonetest Tallinnas - end. Kalinini nimeline tehas, Eesti Meremuuseumi alal asuv hoone, Volta tehase hooned Tööstuse tänaval, Keraamikatehase hooned Maleva 2, Patarei vangla, Tina tänava juugendvilla (projekteerijad Karl Burman ja Artur Perna), puitelamu Kadriorus Poska 6

  1. Kaduvusele kalduvad alternatiivid majas nr. 0 / Andreas Trossek

    Index Scriptorium Estoniae

    Trossek, Andreas, 1980-

    2002-01-01

    Prantsuse kunstnikekoloonia (Delphine Reist, Laurent Faulon, Sebastien Perroud) ja viiuldaja Mathieu Werchowsky Tallinnas valminud installatsiooninäitus "Neli laulu Siivile" vanas Kalinini tehasehoones 7.-12. juunini. Kunstnikud jätavad installatsiooni saatuse hooleks ja lähevad mujale

  2. Synthesis, molecular structure and magnetic properties of a rhenium(IV) compound with catechol

    Science.gov (United States)

    Cuevas, A.; Geis, L.; Pintos, V.; Chiozzone, R.; Sanchíz, J.; Hummert, M.; Schumann, H.; Kremer, C.

    2009-03-01

    A novel Re(IV) complex containing catechol as ligand has been prepared and characterized. The crystal structure of (HNEt 3)(NBu 4)[ReCl 4(cat)]·H 2cat was determined. The rhenium ion presents a distorted octahedral geometry, being bonded to a bidentate catecholate group and four chloride anions. The magnetic properties of the complex were studied, a /2 D/ (the energy gap between ±3/2 and ±1/2 Kramers doublets) value of 190(10) cm -1. This is the largest /2 D/ value reported for Re(IV) up to now.

  3. Rhenium(IV) compounds inducing apoptosis in cancer cells.

    Science.gov (United States)

    Martínez-Lillo, José; Mastropietro, Teresa F; Lappano, Rosamaria; Madeo, Antonio; Alberto, Marta E; Russo, Nino; Maggiolini, Marcello; De Munno, Giovanni

    2011-05-14

    The anticancer properties of a series of mononuclear Re(IV) compounds of formula ReCl(4)L (where L is bpy = 2,2'-bipyridine; bpym = 2,2'-bipyrimidine; dmbpy = 4,4'-dimethyl-2,2'-bipyridine; phen = 1,10-phenanthroline) were investigated for the first time. All compounds displayed potent in vitro antiproliferative activity against selected cancer cells.

  4. X-ray structure of [ReCl4(mu-ox)Cu(pyim)2]: a new heterobimetallic Re(IV)Cu(II) ferrimagnetic chain.

    Science.gov (United States)

    Martínez-Lillo, José; Armentano, Donatella; De Munno, Giovanni; Lloret, Francesc; Julve, Miguel; Faus, Juan

    2008-01-01

    A new heterobimetallic Re(IV)Cu(II) compound has been prepared and its crystal structure determined by single-crystal X-ray diffraction; magnetic susceptibility measurements show that this compound behaves as a ferrimagnetic chain with significant antiferromagnetic interactions between Re(IV) and Cu(II) metal ions.

  5. Rhenium(IV)-copper(II) heterobimetallic complexes with a bridge malonato ligand. Synthesis, crystal structure, and magnetic properties.

    Science.gov (United States)

    Cuevas, Alicia; Chiozzone, Raúl; Kremer, Carlos; Suescun, Leopoldo; Mombrú, Alvaro; Armentano, Donatella; De Munno, Giovanni; Lloret, Francesc; Cano, Juan; Faus, Juan

    2004-11-29

    The Re(IV) complex [ReCl4(mal)]2-, in the form of two slightly different salts, (AsPh4)1.5(HNEt3)0.5[ReCl4(mal)] (1a) and (AsPh4)(HNEt3)[ReCl4(mal)] (1b), and the Re(IV)-Cu(II) bimetallic complexes [ReCl4(mu-mal)Cu(phen)2].CH3CN (2), [ReCl4(mu-mal)Cu(bpy)2] (3), and [ReCl4(mu-mal)Cu(terpy)] (4) (mal=malonate dianion, AsPh4=tetraphenylarsonium cation, HNEt3=triethylammonium cation, phen=1,10-phenanthroline, bpy=2,2'-bipyridine and terpy=2,2':6',2' '-terpyridine) have been synthesized and the structures of 1a, 1b, 2, and 3 determined by single-crystal X-ray diffraction. The structures of 1a and 1b are made up of discrete [ReCl4(mal)]2- anions and AsPh4+ and HNEt3+ cations, held together by electrostatic forces and hydrogen bonds. The Re(IV) atom is surrounded by four chloride anions and a bidentate malonate group, in a distorted octahedral environment. The structure of 2 consist of neutral dinuclear units [ReCl4(mu-mal)Cu(phen)2], with the metal ions united through a bridge carboxilato. The environment of Re(IV) is nearly identical to that in the mononuclear complex, and Cu(II) is five coordinate, being surrounded by four nitrogen atoms of two bidentate phen ligands and one oxygen atom of the malonato ligand. In 3, there are also dinuclear units, [ReCl4(mu-mal)Cu(bpy)2], but the Cu(II) ions complete a distorted octahedral coordination by binding with the free malonato oxygen atom of a neighbor unit, resulting in an infinite chain. The magnetic properties of 1-4 were also investigated in the temperature range 2.0-300 K. The magnetic behavior of 1a and 1b is as expected for a Re(IV) complex with a large value of the zero-field splitting (2D ca. 110 cm(-1)). For the bimetallic complexes, the magnetic coupling between Re(IV) and Cu(II) is antiferromagnetic in 2 (J=-0.39 cm(-1)), ferromagnetic in 4 (J=+1.51 cm(-1)), and nearly negligible in 3 (J=-0.09 cm(-1)).

  6. Heterobimetallic oxalato-bridged M(II)Re(IV) complexes (M = Mn, Fe, Co, Ni): synthesis, crystal structure, and magnetic properties.

    Science.gov (United States)

    Chiozzone, Raúl; González, Ricardo; Kremer, Carlos; De Munno, Giovanni; Armentano, Donatella; Lloret, Francesc; Julve, Miguel; Faus, Juan

    2003-02-24

    Four rhenium(IV)-M(II) bimetallic complexes of formula [ReCl(4)(mu-ox)M(dmphen)(2)].CH(3)CN with M = Mn (1), Fe (2), Co (3), and Ni (4) (ox = oxalate anion, dmphen = 2,9-dimethyl-1,10-phenanthroline) have been synthesized and the crystal structures of 1 and 3 determined by single-crystal X-ray diffraction. 1 and 3 are isostructural and crystallize in the monoclinic system, space group P2(1)/c, with a = 16.008(4) A, b = 12.729(2) A, c = 18.909(5) A, beta = 112.70(2) degrees, and Z = 4 for 1 and a = 15.998(4) A, b = 12.665(2) A, c = 18.693(5) A, beta = 112.33(2) degrees, and Z = 4, for 3. The structure of 1 and 3 is made up of neutral [ReCl(4)(mu-ox)M(dmphen)(2)] bimetallic units (M = Mn (1), Co (3)) and acetonitrile molecules of crystallization. M(II) and Re(IV) metal ions exhibit distorted octahedral coordination geometries being bridged by a bis(bidentate) oxalato ligand. The magnetic behavior of 1-4 has been investigated over the temperature range 2.0-300 K. A very weak antiferromagnetic coupling between Re(IV) and Mn(II) occurs in 1 (J = -0.1 cm(-)(1)), whereas a significant ferromagnetic interaction between Re(IV) and M(II) is observed in 2-4 [J = +2.8 (2), +5.2 (3), and +5.9 cm(-)(1) (4)].

  7. New family of thiocyanate-bridged Re(IV)-SCN-M(II) (M = Ni, Co, Fe, and Mn) heterobimetallic compounds: synthesis, crystal structure, and magnetic properties.

    Science.gov (United States)

    González, Ricardo; Acosta, Alvaro; Chiozzone, Raúl; Kremer, Carlos; Armentano, Donatella; De Munno, Giovanni; Julve, Miguel; Lloret, Francesc; Faus, Juan

    2012-05-21

    The heterobimetallic complexes of formula [(Me(2)phen)(2)M(μ-NCS)Re(NCS)(5)]·CH(3)CN [Me(2)phen = 2,9-dimethyl-1,10-phenanthroline and M = Ni (1), Co (2), Fe (3), and Mn (4)] have been prepared, and their crystal structures have been determined by X-ray diffraction on single crystals. Compounds 1-4 crystallize in the monoclinic C2/c space group, and their structure consists of neutral [(Me(2)phen)(2)M(μ-NCS)Re(NCS)(5)] heterodinuclear units with a Re-SCN-M bridge. Each Re(IV) ion in this series is six-coordinated with one sulfur and five nitrogen atoms from six thiocyanate groups building a somewhat distorted octahedral environment, whereas the M(II) metal ions are five-coordinated with four nitrogen atoms from two bidentate Me(2)phen molecules and a nitrogen atom from the bridging thiocyanate describing distorted trigonal bipyramidal surroundings. The values of the Re···M separation through the thiocyanate bridge in 1-4 vary in the range 5.903(1)-6.117(3) Å. The magnetic properties of 1-4 as well as those of the parent mononuclear Re(IV) compounds (NBu(4))(2)[Re(NCS)(6)] (A1) (NBu(4)(+) = tetra-n-butylammonium cation) and [Zn(NO(3))(Me(2)phen)(2)](2)[Re(NCS)(5)(SCN)] (A2) were investigated in the temperature range 1.9-300 K. Weak antiferromagnetic interactions between the Re(IV) and M(II) ions across the bridging thiocyanate were found in 1-4 [J = -4.3 (1), -2.4 (2), -1.8 (3), and -1.2 cm(-1) (4), the Hamiltonian being defined as Ĥ = -JŜ(Re)·Ŝ(M)]. The magnetic behavior of A2 is that of a magnetically diluted Re(IV) complex with a large and positive value of the zero-field splitting for the ground level (D(Re) = +37.0 cm(-1)). In the case of A1, although its magnetic behavior is similar to that of A2 in the high-temperature range (D(Re) being +19.0 cm(-1)), it exhibits a weak ferromagnetism below 3.0 K with a canting angle of 1.3°.

  8. Ferromagnetic coupling and spin canting behaviour in heterobimetallic Re(IV)M(II/III) (M = Co(II/III), Ni(II)) species.

    Science.gov (United States)

    Martínez-Lillo, José; Armentano, Donatella; De Munno, Giovanni; Julve, Miguel; Lloret, Francesc; Faus, Juan

    2013-02-01

    Three novel heterobimetallic Re(IV) compounds of formulae [ReBr(4)(μ-ox)M(4,7-Cl(2)phen)(2)]·CH(3)CN·CH(3)NO(2) [M = Co(II) (1) and Ni(II) (2)] and [ReBr(4)(ox)](3)[Co(III)(5,6-dmphen)(3)](2)·CH(3)CN·2CH(3)NO(2)·4H(2)O (3) [ox = oxalate, 4,7-Cl(2)phen = 4,7-dichloro-1,10-phenanthroline and 5,6-dmphen = 5,6-dimethyl-1,10-phenanthroline] have been synthesised and the structures of 1 and 3 determined by single crystal X-ray diffraction. Compound 1 is an oxalato-bridged Re(IV)Co(II) heterodinuclear complex where the [ReBr(4)(ox)](2-) unit acts as a bidentate ligand towards the [Co(4,7-Cl(2)phen)(2)](2+) entity, the separation between Re(IV) and Co(II) across the oxalate being 5.482(1) Å. Compound 3 is an ionic salt whose structure is made up of [Re(IV)Br(4)(ox)](2-) anions and [Co(III)(5,6-dmphen)(3)](3+) cations plus acetonitrile, nitromethane and water as solvent molecules. The magnetic properties of 1-3 were investigated in the temperature range 1.9-300 K. Relatively large ferromagnetic interactions between Re(IV) and M(II) through the bis(bidentate) oxalato occur in 1 and 2 [J(ReM) = +11.0 (1) and +12.2 cm(-1) (2), the Hamiltonian being defined as Ĥ = -J(ReM)Ŝ(Re)·Ŝ(M)] which are explained on the basis of orbital symmetry considerations. A behaviour typical of a magnetically diluted Re(IV) complex with a large and positive value of zero-field splitting for the ground level (D(Re) = +43 cm(-1)) is observed for 3 in the high temperature range, whereas it exhibits spin canting in the low temperature domain as well as magnetic ordering below ca. 4.8 K.

  9. A Chiral, Photoluminescent, and Spin-Canted {Cu(I)Re(IV)2}n Branched Chain.

    Science.gov (United States)

    Martínez-Lillo, José; Armentano, Donatella; Fortea-Pérez, Francisco R; Stiriba, Salah-Eddine; De Munno, Giovanni; Lloret, Francesc; Julve, Miguel; Faus, Juan

    2015-05-18

    A new heteroleptic 1D Cu(I)-Re(IV) coordination polymer of the formula {Cu(I)Re(IV)Cl4(μ-Cl)(μ-pyz)[Re(IV)Cl4(μ-bpym)]}n·nMeNO2 (1; pyz = pyrazine, bpym = 2,2'-bipyrimidine) has been prepared through the Cu(I)-mediated self-assembly of two different Re(IV) metalloligands, namely, [ReCl5(pyz)](-) and [ReCl4(bpym)]. 1 consists of chiral branched chains with an overall rack-type architecture displaying photoemission and magnetic ordering. These results constitute a first step toward making new multifunctional magnetic materials based on mixed 3d-5d molecular systems.

  10. A novel series of rhenium-bipyrimidine complexes: synthesis, crystal structure and electrochemical properties.

    Science.gov (United States)

    Chiozzone, Raúl; González, Ricardo; Kremer, Carlos; Cerdá, María Fernanda; Armentano, Donatella; De Munno, Giovanni; Martínez-Lillo, José; Faus, Juan

    2007-02-14

    Four novel rhenium complexes of formula [ReCl(4)(bpym)] (1), [ReBr(4)(bpym)] (2) PPh(4)[ReCl(4)(bpym)] (3) and NBu(4)[ReBr(4)(bpym)] (4) (bpym = 2,2'-bipyrimidine, PPh(4) = tetraphenylphosphonium cation and NBu(4) = tetrabutylammonium cation), have been synthesized and their crystal structures determined by single-crystal X-ray diffraction. The structures of 1 and 2 consist of [ReX(4)(bpym)] molecules held together by van der Waals forces. In both complexes the Re(iv) central atom is surrounded by four halide anions and two nitrogen atoms of a bpym bidentate ligand in a distorted octahedral environment. The structures of 3 and 4 consist of [ReX(4)(bpym)](-) anions and PPh(4)(+) () or NBu(4)(+) (4) cations. The coordination sphere of the Re(iii) metal ion is the same as in 1 and 2, respectively. However, whereas the Re-X bonds are longer the Re-N bonds are shorter than in 1 and 2. This fact reveals that the bpym ligand forms a stronger bond with Re(iii) than with Re(iv) resulting in a stabilisation of the lower oxidation state. [ReX(4)(bpym)] complexes are easily reduced, chemically and electrochemically, to the corresponding [ReX(4)(bpym)](-) anions. A voltammetric study shows that the electron transference is a reversible process characterized by formal redox potentials of +0.19 V (1) and +0.32 V (2) vs. NHE, in acetonitrile as solvent.

  11. Synthesis, crystal structure and magnetic properties of novel heterobimetallic malonate-bridged MIIReIV complexes (M = Mn, Fe, Co and Ni).

    Science.gov (United States)

    Cuevas, Alicia; Kremer, Carlos; Suescun, Leopoldo; Russi, Silvia; Mombrú, Alvaro W; Lloret, Francesc; Julve, Miguel; Faus, Juan

    2007-12-07

    Five novel ReIV-MII bimetallic complexes of formula [ReCl4(mu-mal)M(dmphen)2].MeCN [M = Co (1), Fe (2) and Ni (3)], [ReCl4(mu-mal)Ni(dmphen)(MeCN)2(H2O)].(MeCN)0.5(H2O)0.5 (4), and [ReCl4(mu-mal)Mn(dmphen)(H2O)2].dmphen.MeCN.H2O (5) (mal = malonate dianion, dmphen = 2,9-dimethyl-1,10-phenanthroline) have been synthesized, and the structures of 1, 2, 4, and 5 determined by single-crystal X-ray diffraction. The structures of 1 and 2 consist of neutral [ReCl4(mu-mal)M(dmphen)2] dinuclear units where the metal ions are linked through a malonate ligand which adopts simultaneously the bidentate (at ReIV) and monodentate (at MII) coordination modes. The bridging carboxylate-malonate group in them exhibits the anti-syn conformation. The rhenium atom is six-coordinated with four chloro atoms and two carboxylate-oxygens from a bidentate malonate group in a distorted octahedral environment. The M atom is five-coordinated being surrounded by four nitrogen atoms of two bidentate dmphen ligands and one oxygen atom of the malonato ligand. There are also ReIV(mu-mal)NiII dinuclear units in 4 with the same type of bridge, but the nickel atom is six-coordinated with one bidentate dmphen, two molecules of acetonitrile and one water molecule as peripheral ligands. Compound 5 is a neutral chain compound with regular alternating rhenium(IV) and manganese(II) ions. The [ReCl4(mal)]2- units in each chain act as bismonodenate ligands through two carboxylate-oxygen atoms toward [Mn(dmphen)(H2O)2]2+ entities. Variable-temperature magnetic measurements of 1-5 in the temperature range 2.0-300 K show the occurrence of weak antiferromagnetic interactions which are rationalized on the basis of the structural knowledge and simple orbital considerations. Very noticeable is compound 5, a ferrimagnetic chain with regular alternating ReIV and MnII cations.

  12. Synthesis, Crystal Structure, and Magnetic Properties of Tetraphenylarsonium Tetrachloro(oxalato)rhenate(IV) and Bis(2,2'-bipyridine)tetrachloro(&mgr;-oxalato)copper(II)rhenium(IV).

    Science.gov (United States)

    Chiozzone, Raúl; González, Ricardo; Kremer, Carlos; De Munno, Giovanni; Cano, Joan; Lloret, Francesc; Julve, Miguel; Faus, Juan

    1999-10-18

    Two new rhenium(IV) compounds of formula (AsPh(4))(2)[ReCl(4)(ox)] (1) and [ReCl(4)(&mgr;-ox)Cu(bipy)(2)] (2) (AsPh(4) = tetraphenylarsonium cation, ox = oxalate anion, and bipy = 2,2'-bipyridine) have been synthesized and their crystal structures determined by single-crystal X-ray diffraction. 1 and 2 crystallize in the monoclinic system, space groups P2(1)/c and P2(1)/n, respectively, with a = 22.250(5) Å, b = 11.245(3) Å, c = 19.089(4) Å, beta = 96.59(2) degrees, and Z = 4 for 1 and a = 9.421(2) Å, b = 16.909(4) Å, c = 16.179(4) Å, beta = 93.97(2) degrees, and Z = 4 for 2. The structure of 1 is made up of [ReCl(4)(ox)](2)(-) anions and AsPh(4)(+) cations held united by electrostatic forces. Rhenium(IV) is hexacoordinate, with two oxygens of a chelating ox and four chlorine atoms building a distorted octahedron around the metal atom. There is no contact between the [ReCl(4)(ox)](2)(-) anions, the shortest Re.Re and Cl.Cl distances being 10.345 and 7.209 Å, respectively. This anionic complex is coordinated to a [Cu(bipy)(2)](2+) cation in 2, through one oxalate-oxygen, giving a neutral heterometallic dinuclear unit. The Cu(II) ion shows a very distorted five-coordinated geometry, four bipy-nitrogens occuping the equatorial positions and the oxygen atom the apical one. The basal plane geometry is distorted toward the tetrahedron, the dihedral angle between the mean planes of the two bipy ligands is 37.6(2) degrees. These [ReCl(4)(&mgr;-ox)Cu(bipy)(2)] units are arranged in such a way that a chlorine atom of one of them points toward the copper atom of the neighboring one, forming helicoid chains. The intrachain Re.Cu distances through chloro and oxalato bridges are 4.658 and 4.798 Å, respectively. The magnetic behavior of 1 and 2 has been investigated over the temperature range 1.8-300 K. 1 is a magnetically diluted Re(IV) complex, the great value of zero-field splitting of the ground level (D = 60 cm(-)(1)) accounting for the variation of chi(M)T with T in

  13. Slow magnetic relaxation induced by a large transverse zero-field splitting in a Mn(II)Re(IV)(CN)2 single-chain magnet.

    Science.gov (United States)

    Feng, Xiaowen; Liu, Junjie; Harris, T David; Hill, Stephen; Long, Jeffrey R

    2012-05-02

    The model compounds (NBu(4))(2)[ReCl(4)(CN)(2)] (1), (DMF)(4)ZnReCl(4)(CN)(2) (2), and [(PY5Me(2))(2)Mn(2)ReCl(4)(CN)(2)](PF(6))(2) (3) have been synthesized to probe the origin of the magnetic anisotropy barrier in the one-dimensional coordination solid (DMF)(4)MnReCl(4)(CN)(2) (4). High-field electron paramagnetic resonance spectroscopy reveals the presence of an easy-plane anisotropy (D > 0) with a significant transverse component, E, in compounds 1-3. These findings indicate that the onset of one-dimensional spin correlations within the chain compound 4 leads to a suppression of quantum tunneling of the magnetization within the easy plane, resulting in magnetic bistability and slow relaxation behavior. Within this picture, it is the transverse E term associated with the Re(IV) centers that determines the easy axis and the anisotropy energy scale associated with the relaxation barrier. The results demonstrate for the first time that slow magnetic relaxation can be achieved through optimization of the transverse anisotropy associated with magnetic ions that possess easy-plane anisotropy, thus providing a new direction in the design of single-molecule and single-chain magnets.

  14. Dissimilar behavior of technetium and rhenium in borosilicatewaste glass as determined by X-ray absorption spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Lukens, Wayne W.; McKeown, David A.; Buechele, Andrew C.; Muller,Isabelle S.; Shuh, David K.; Pegg, Ian L.

    2006-11-09

    Technetium-99 is an abundant, long-lived (t1/2 = 213,000 yr)fission product that creates challenges for the safe, long-term disposalof nuclear waste. While 99Tc receives attention largely due to its highenvironmental mobility, it also causes problems during its incorporationinto nuclear waste glass due to the volatility of Tc(VII) compounds. Thisvolatility decreases the amount of 99Tc stabilized in the waste glass andcauses contamination of the waste glass melter and off-gas system. Theapproach to decrease the volatility of 99Tc that has received the mostattention is reduction of the volatile Tc(VII) species to less volatileTc(IV) species in the glass melt. On engineering scale experiments,rhenium is often used as a non-radioactive surrogate for 99Tc to avoidthe radioactive contamination problems caused by volatile 99Tc compounds.However, Re(VII) is more stable towards reduction than Tc(VII), so morereducing conditions would be required in the glass melt to produceRe(IV). To better understand the redox behavior of Tc and Re in nuclearwaste glass, a series of glasses were prepared under different redoxconditions. The speciation of Tc and Re in the resulting glasses wasdetermined by X-ray absorption fine structure spectroscopy. Surprisingly,Re and Tc do not behave similarly in the glass melt. Although Tc(0),Tc(IV), and Tc(VII) were observed in these samples, only Re(0) andRe(VII) were found. In no case was Re(IV) (or Re(VI))observed.

  15. Highly anisotropic rhenium(IV) complexes: new examples of mononuclear single-molecule magnets.

    Science.gov (United States)

    Martínez-Lillo, José; Mastropietro, Teresa F; Lhotel, Elsa; Paulsen, Carley; Cano, Joan; De Munno, Giovanni; Faus, Juan; Lloret, Francesc; Julve, Miguel; Nellutla, Saritha; Krzystek, J

    2013-09-18

    The rhenium(IV) complex (NBu4)2[ReBr4(ox)] (1) (ox = oxalate and NBu4(+) = tetra-n-butylammonium cation) has been prepared and its crystal structure determined by X-ray diffraction. The structure is made up of discrete [ReBr4(ox)](2-) anions and bulky NBu4(+) cations. Each [ReBr4(ox)](2-) anion is surrounded by six NBu4(+) cations, which preclude any significant intermolecular contact between the anionic entities, the shortest rhenium···rhenium distance being 9.373(1) Å. Variable temperature dc and ac magnetic susceptibility measurements and field-dependent magnetization experiments on polycrystalline samples of 1 reveal the occurrence of highly anisotropic magnetically isolated Re(IV) centers (S(Re) = 3/2), which exhibit slow relaxation of the magnetization at very low temperatures in a dc field. Ac measurements conducted on a polycrystalline sample of the complex (NBu4)2[ReCl4(ox)] (2) [compound isostructural to 1 whose structure and dc magnetic susceptibility study were previously reported in Tomkiewicz, A.; Bartczak, T. J.; Kruszyński, R.; Mroziński, J. J. Mol. Struct. 2001, 595, 225] show a similar behavior, both complexes thus constituting new examples of mononuclear single-molecule magnets. High-frequency and -field electron paramagnetic resonance on polycrystalline samples of 1 and 2 and on single crystals of 2 allowed for the determination for the first time of the negative sign and confirmed a significant magnitude and rhombicity (E/D) of the zero-field splitting tensor of the [ReCl4(ox)](2-) and [ReBr4(ox)](2-) centers, originating from a combination of spin-orbit coupling and low molecular symmetry. D and E values of 1 and 2 were estimated through magnetization measurements and theoretically calculated through complete active space and density functional theory methodologies.

  16. Mixed chloride/phosphine complexes of the dirhenium core. 10. Redox reactions of an edge-sharing dirhenium(III) non-metal-metal-bonded complex, Re(2)(mu-Cl)(2)Cl(4)(PMe(3))(4).

    Science.gov (United States)

    Cotton, F A; Dikarev, E V; Petrukhina, M A

    2001-12-17

    Reduction and oxidation reactions of the dirhenium(III) non-metal-metal-bonded edge-sharing complex, Re(2)(mu-Cl)(2)Cl(4)(PMe(3))(4) (1), have been studied. Several new mono- and dinuclear rhenium compounds have been isolated and structurally characterized in the course of this study. Reductions of 1 with 1 and 2 equiv of KC(8) result in an unusual face-sharing complex having an Re(2)(5+) core, Re(2)(mu-Cl)(3)Cl(2)(PMe(3))(4) (2), and a triply bonded Re(II) compound, 1,2,7,8-Re(2)Cl(4)(PMe(3))(4) (3), respectively. Two-electron reduction of 1 in the presence of tetrabutylammonium chloride affords a new triply bonded complex of the Re(2)(4+) core, [Bu(n)()(4)N][1,2,7-Re(2)Cl(5)(PMe(3))(3)] (4). Oxidation of 1 with NOBF(4) yields a Re(IV) mononuclear compound, trans-ReCl(4)(PMe(3))(2) (5). Two isomers of the monomeric Re(III) anion, [ReCl(4)(PMe(3))(2)](-) (6, 7), have been isolated as side products. The crystal structures of compounds 2 and 4-7 have been determined by X-ray crystallography. The Re-Re distance in the face-sharing complex 2 of 2.686(1) A is relatively short. The metal-metal bond length in anion 4 of 2.2354(7) A is consistent with the usual values for the triply bonded Re(2)(4+) core compounds. In addition, a cis arrangement of trimethylphosphine ligands in the starting material 1 is retained upon reduction in the dinuclear products 2-4.

  17. Technetium (VII) Co-precipitation with Framework Aluminosilicates

    Energy Technology Data Exchange (ETDEWEB)

    Harsh, James B. [Washington State Univ., Pullman, WA (United States); Dickson, Johnbull Otah [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Pierce, Eric M. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Bargar, John [SLAC National Accelerator Lab., Menlo Park, CA (United States)

    2015-07-13

    Technetium-99 (99Tc), a long-lived radionuclide, is one of the most widespread contaminants within the Hanford subsurface. At some depths, it is only extractable with strong acids, suggesting incorporation into a solid phase. We hypothesized that Tc may have coprecipitated with feldspathoid aluminosilicates under waste tanks that had leaked caustic solutions into the vadose zone. Our objectives were to determine if Tc could be incorporated into the feldspathoids cancrinite and sodalite and under what conditions coprecipitation could occur. Our hypothesis was that sodalite was more likely to incorporate and retain Tc. Our approach was to use known methods of feldspathoid formation in solutions resembling those in Hanford waste tanks contacting sediments in terms of major ion (Na, NO3, OH, Al(OH)4, and Si(OH)4 concentrations. In some cases, Al and Si were supplied from zeolite. We used perrhenate (ReO4) as a surrogate for pertechnetate (TcO4) to avoid the radioactivity. The major findings of this study were 1) ReO4 could be incorporated into either sodalite or cancrinite but the concentration in the solid was < 1% of the competing ion Cl, NO3, or NO2. 2) The small amount of ReO4 incorporated was not exchangeable with NO3 or NO2. 3) In sodalite, NO3 was highly preferred over ReO4 but significant Re-sodalite was formed when the mole fraction in solution (Re/Re+N) exceeded 0.8. 4) A nonlinear relation between the unit cell parameter and amount of Re incorporated suggested that a separate Re-sodalite phase was formed rather than a solid solution. 5) We determined that sodalite preference for sodalite in the presence of different anions increased with the ionic size of the competing anion: Cl < CO3 < NO3 < SO4 < MnO4 < WO4 and significant incorporation did not occur unless the difference in anion radii was less than 12%. 6) Re(VII) was not significantly reduced to Re(IV) under the conditions of this experiment and Re appeared to be a good surrogate for Tc under oxidizing

  18. Magnetic studies on hexaiodorhenate(IV) salts of univalent cations. Spin canting and magnetic ordering in K2[ReI6] with Tc = 24 K.

    Science.gov (United States)

    González, Ricardo; Chiozzone, Raúl; Kremer, Carlos; De Munno, Giovanni; Nicolò, Francesco; Lloret, Francesc; Julve, Miguel; Faus, Juan

    2003-04-21

    The ionic salts of rhenium(IV) of formula (Cat)(2)[ReI(6)] with Cat = Li(+) (1), Na(+) (2), K(+) (3), Rb(+) (4), Cs(+) (5), NH(4)(+) (6), and AsPh(4)(+) (7) [AsPh(4)(+) = tetraphenylarsonium cation] have been synthesized, and the structures of two of them (namely, 3 and 6) were determined by single-crystal X-ray diffraction. 3 crystallizes in the monoclinic system, space group Pn, with a = 7.815(1) A, b = 7.874(1) A, c = 11.335(1) A, beta = 90.38(1) degrees, and Z = 2 whereas 6 crystallizes in the tetragonal system, space group P4/mnc, with a = 7.881(1) A, b = 7.881(1) A, c = 11.474(2) A, and Z = 2. The structures of 3 and 6 are made up of discrete [ReI(6)](2)(-) anions and K(+) (3) or NH(4)(+) (6) cations held together by electrostatic forces (3 and 6) and N-H.I hydrogen bonds (6). The rhenium(IV) cation in 3 and 6 is surrounded by six iodide ligands in an octahedral environment with the Re-I bond lengths varying in a very narrow range [2.704(3)-2.738(3) and 2.716(1)-2.722(2) A for 3 and 6, respectively]. The [ReI(6)](2)(-) anions in 6 describe a tetragonally distorted body-centered cubic structure. In 3, the arrangement of these units is similar but more distorted. The different arrangement of the anions in 3 and 6 accounts for the centrosymmetric (6) and non-centrosymmetric (3) structures observed. The magnetic properties of 1-7 were investigated in the temperature range 2.0-300 K. The magnetic behavior of 7 is that of a magnetically diluted Re(IV) complex with a large value of the zero-field splitting of the ground level (|2D| = 49.8 cm(-)(1)) whereas those of 1, 2, and 4-6 are typical of antiferromagnetically coupled systems with susceptibility maxima at 28 (1), 27 (2), 21 (4), 16 (5), and 20 K (6). In the case of compound 3, its magnetic behavior in the high-temperature range is parallel to that observed in the parent salts but below 24 K it is a weak ferromagnet with a canting angle of ca. 1.2 degrees.