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'Sulfur Ligands' in keywords Facet   section ZfN Section B  [X]
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1Author    Dieter Sellmann+, Bernd Seubert, W. Olfgang Kern, Falk Knoch, M. Atthias, MollRequires cookie*
 Title    Übergangsmetallkomplexe mit Schwefelliganden, LXIX* and X-Ray Structure Analyses  
 Abstract    Chrom-und Wolfram-Nitrosyl-Komplexe mit schwefeldominierten Koordinationssphären: IC r(N O)XS4')]v (x = 1, y = 2; x = 2, y = 1), (NR4)2[W (NO)2(S 2)2] (R = M e, /i-Bu), [W(L)(NO)('S4)] (L = NO , N P M e3, NPEt3) und [//-0 { W (N 0)(S4)} 2] ('S2'2" = l,2-Benzoldithiolat(2-); 'S4'2-= l,2-Bis(2-mercaptophenylthio)ethan(2-)); Synthesen, Eigenschaften und Röntgenstrukturanalysen Transition M etal Complexes with Sulfur Ligands, LXIX* Chromium and Tungsten Nitrosyl Complexes with Sulfur Dom inated C oordination Spheres: [C r(N O)/S 4')]v(* = \ , y = 2 \x = 2 , y = 1), (N R 4)2[W(NO)2('S2')2] (R = Me, «-Bu), [W(L)(NO)('S4')] (L = NO, N PM e3, N P E t3) and [//-0{W (N 0)('s7)}2] ('S2'2-= 1.2-B enzenedithiolate(2-);'S4'2-= 1.2-Bis(2-mercaptophenylthio)ethane(2-)); Syntheses, Properties In order to study the properties o f sulfur coordinated metal centres, the chromium and tung­ sten complexes [Cr(NO)(//-'S4% (4), (N R 4),[W (N O)2('S 0 2] (1) (R = Me (la), «-Bu (lb)), [W (NO)2('S4')] (2), [^ -0 {W (N 0)('S 4')}2] (3) and [W (N PR 3)(N O)('S4')] (5) (R = Me (5a), Et (5b)) were synthesized ('S2'2 = 1,2-benzenedithiolate(2—) ; 'S4'2 = 1,2-bis(2-mercaptophenyl-th io)ethane(2-)). la and lb result from the reductive nitrosylation o f Li2[W('S2')3] which was prepared by reduction o f [W('S2')3] with rc-BuLi. la was also obtained from [W (NO)2(Cl)2]", 'S2'2-and N M e4+. Alkylation o f la or lb by 1.2-dibromoethane yields 2, whose X-ray structure 
  Reference    Z. Naturforsch. 46b, 1435—5 (1991); eingegangen am 8. A pril/ 8. Juli 1991 
  Published    1991 
  Keywords    Chromium, Tungsten, Nitrosyl Complexes, Sulfur Ligands, X-Ray 
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 TEI-XML for    default:Reihe_B/46/ZNB-1991-46b-1435.pdf 
 Identifier    ZNB-1991-46b-1435 
 Volume    46 
2Author    WolfdieterA. Schenk, Nikolai KuhnertaRequires cookie*
 Title    Synthesis of Halfsandwich Ruthenium Complexes of Sulfinic Acid Esters [1]  
 Abstract    A series of halfsandwich ruthenium sulfinato complexes [CpRu(PR'3)2(SO:R)] (R = Me, CH 2Ph, C2H4Ph, Ph, 4 -CöH4Me; PR'3 = PM e3, 1/2 dppm) with various electronic and steric environments around the ruthenium centre, have been prepared by insertion of SO2 into a ruthenium carbon bond, by a direct ligand exchange reaction, or by oxidation of thiolato complexes with 3-chloroperoxybenzoic acid. The chiral complexes [CpRu(C0)(PPh3)(S0 2 R)] (R = Me, CH2Ph, Ph) were obtained similarly by oxidation of the corresponding thiolates with magnesium monoperoxyphthalate. Alkylation of the sulfinato complexes with oxonium salts [Rm 3 0 ]X (R" = Me, Et; X = B F 4 , PF6) gave ruthenium complexes of sulfinic acid esters, [C pRu(L)(L')(S(0)(0R ")R)]X in high yields and, for the chiral complexes, up to 82% de. The esters may be detached from the metal by ligand exchange with acetonitrile. Stronger nucleophiles such as I~ or SMe~ dealkylate the coordinated sulfinic acid esters. 
  Reference    Z. Naturforsch. 55b, 527—535 (2000); received March 20 2000 
  Published    2000 
  Keywords    Ruthenium Complexes, Sulfur Ligands, Diastereoselective Alkylations 
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 TEI-XML for    default:Reihe_B/55/ZNB-2000-55b-0527.pdf 
 Identifier    ZNB-2000-55b-0527 
 Volume    55 
3Author    Dieter Sellmann, Daniel Häußinger, Torsten Gottschalk-Gaudig, FrankW. HeinemannRequires cookie*
 Title    Übergangsmetallkomplexe Activated CH2 Groups, and Interionic Interactions in the Solid State ('pybuS4'2-= 2,6-Bis(2-mercapto-3,5-di-terf-butylphenylthio)dimethylpyridine(2-))  
 Abstract    mit Schwefelliganden, 145 [1]. [Ru(NO)(,py^M S4 ,)]Br, ein Komplex mit [Ru(NO)(NS4)]-Gerüst, aktivierten CH2-Gruppen und interionischen Wechselwirkungen im Festkörper ['p y ^ S ^ 2* = 2,6-Bis(2-mercapto-3,5-di-terM>utyl-phenylthio)dimethylpyridin(2-)] Transition Metal Complexes with Sulfur Ligands, 145 [1]. [Ru(NO)('pybuS4')]Br, a Complex with [Ru(NO)(NS4)] Core, In the search for soluble and reactive ruthenium nitrosyl complexes, [Ru(NO)('pybuS4')]Br ([2]Br) was synthesized by template alkylation of NBu4[Ru(NO)('buS2')2] with py(CH',Br)2 ['pybuS4'2-= 2,6-bis(2-mercapto-3,5-di-ter/-butyl-phenylthio)dimethylpyridine(2-); '°US2 = 2-mercapto-3,5-di-terf-butylphenylthiolate(2-); py(CH2Br)2 = 2,6-bis(bromomethyl)pyridine]. The solid state structure of 2 has been determined by X-ray diffraction, which reveals a head-to-head 0 -0 interaction between the linear Ru-NO entities. The ligand CH 2 protons of [2]+ are activated and exchange with D+ under ambient conditions. The /^(NO) band of [2]Br appears at 1841 cm -1 in the solid state (KBr or hostaflon mull) and is significantly blue-shifted in solution (1879 cm-1 in MeOH, 1886 cm -1 in DMF). A similar blue-shift (1866 cm -1 in KBr vs. 1888 cm -1 in MeOH) has been found for [Ru(NO)('pyS4')lBr ([l]B r) which contains the parent [Ru(NO)('pyS4')]+ cation ['pyS4'2-= 2,6-bis(2-mercaptophenylthio)dimethylpyr-idine(2-)]. These t^(NO) shifts can be explained either by an interionic charge-transfer between the bromide anions and the nitrosyl complex cation or by 0 -0 interactions between two NO ligands as found for solid-state [2]Br. These interactions are not found for [l]O Ts which exhibits a ^(N O) band at ca. 1890 cm -in the solid state (KBr, hostaflon) as well as in MeOH solution. 
  Reference    Z. Naturforsch. 55b, 723—729 (2000); eingegangen am 5. April 2000 
  Published    2000 
  Keywords    Ruthenium Nitrosyl Complexes, Sulfur Ligands, Interionic Interaction 
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 TEI-XML for    default:Reihe_B/55/ZNB-2000-55b-0723.pdf 
 Identifier    ZNB-2000-55b-0723 
 Volume    55 
4Author    AndreasF. Stange, Eberhard Waldhör, Michael Moscherosch, Wolfgang KaimRequires cookie*
 Title    Variable Structure of the Cu2S2 Core in Doubly Thiolate-Bridged Dicopper(I) Complexes. An X-Ray Crystallographic, Electrochemical and EPR Study of (dmp)2 (o-CH3 C6H4S)2Cu2 , dmp = 2,9-Dimethyl-l,10-phenanthroline, and a Comment on the Nature of Phenanthroline-Containing "Cu(0)" Complexes  
 Abstract    The molecular and crystal structure of the dicopper(I) complex (dm p)2(M-o-CH3C6H4S)2Cu2 (1), dmp = 2,9-dim ethyl-l,10-phenanthroline, has been deter­ mined. With Cu/S/Cu and S/Cu/S bond angles between 80 and 100°, the planar structure of the central CuSCuS four-membered ring is much more symmetric for 1 as compared to the analogous complex 2 of unsubstituted 1,10-phenanthroline which has a folded Cu2S2 core with bond angles between 67 and 108°. This result illustrates a considerable structural flexi­ bility of the LCu(m-SR)2CuL entity which is being discussed as a possible model for CuA centers of cytochrome c oxidase or nitrous oxide reductase. Oxidation of both com plexes 1 and 2 remains irreversible even at cyclovoltammetric scan rates o f 1 V/s. However, the methyl substitution in complex 1 causes increased reversibility of the electronically coupled dmp-based reduction processes. Accordingly, the EPR spectrum of l -* is characterized by hyper-fine splitting from dmp--and a relatively small 63 " Cu coupling of 0.53 mT. The stabilization of 2,9-disubstituted 1,10-phenanthroline radical anions by coordination to Cu(I) is also dem ­ onstrated by detection of a single broad EPR line at g 2.0028 for the formal "C u(0)" complex Cu(dpp)2 = CuI(dpp_-)(dpp), dpp = 2,9-diphenyl-l,10-phenanthroline. While the EPR signal of Cu(dpp)2 loses intensity on cooling, possibly due to dimerization and spin-pairing, the distorted tetrahedral configuration with essential orthogonal arrangement of dpp jz systems seem s to disfavour an intramolecular electron hopping. 
  Reference    (Z. Naturforsch. 50b, 115—122 [1995]; received July 25 1994) 
  Published    1995 
  Keywords    Crystal Structure, Copper Complexes, Sulfur Ligands, 1, 10-Phenanthrolines, EPR Spectra 
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 TEI-XML for    default:Reihe_B/50/ZNB-1995-50b-0115.pdf 
 Identifier    ZNB-1995-50b-0115 
 Volume    50