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'Tungsten' in keywords Facet   section ZfN Section B:Volume 046  [X]
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1991 (2)
1Author    Dieter Sellmann+, W. Olfgang Kern, Adelgunde Holzmeier, Georg Pöhlmann, M. Atthias, MollRequires cookie*
 Title    Übergangsmetallkomplexe mit Schwefelliganden, LXVI  
 Abstract    Substitutions-und Additionsreaktionen an Molybdän-und Wolfram-Schwefel-Zentren von |M (Cl)(NO)('S4)], M = Mo, W, mit Thiolaten SR" (R = Me, 'Pr, w Bu, Ph) und PM e3 ('S4'2-= l,2-Bis(2-mercaptophenylthio)ethan(2-)) Transition M etal Complexes with Sulfur Ligands, LXVI* Substitution and A ddition Reactions at M olybdenum and Tungsten Sulfur Centres of [M(Cl)(NO)('S4')], M = M o, W, with Thiolates SR " (R = Me, 'Pr, "Bu, Ph) and PM e3('S4'2~ = l,2-Bis(2-mercaptophenylthio)ethane(2-)) Since substrate addition and elim ination reactions are essential reactions o f metal sulfur centres in oxidoreductases, we investigated the substitution o f chloride in [Mo(C1)(NO)('S4')](1) ('S4'2-= l,2-Bis(2-m ercaptophenylthio)ethane(2-)) [4] and in the anal­ ogous tungsten complex [W (Cl)(NO)('S4')](2). The chloride ligands in 1 and 2 can easily be substituted by thiolates to give [M (SR)(NO)('S4')] (M = M o, R = Me 3a, 'Pr 3b, "Bu 3c, Ph 3d; M = W, R = Me 4 a , Ph 4b). For these substitution reactions an associative mechanism is suggested. The SR~ ligands act probably as o-n four electron donor ligands to give metal centres with an 18 electron configuration as also found in the amido complexes [M o(N R 2)(NO)('S4')] [4]. 1 and 2 react with PM e3 to yield the adducts [M(PMe3)(Cl)(NO)('S4')] (M = Mo 5, W 6), w hose N M R spectra indicate the formation o f two stereoisomers in a ratio o f about 2:3. 
  Reference    Z. Naturforsch. 46b, 1349—1356 (1991); eingegangen am 28. Januar 1991 
  Published    1991 
  Keywords    Sulfur Complexes, Synthesis, Reactions, Stereochemistry, M olybdenum, Tungsten 
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 TEI-XML for    default:Reihe_B/46/ZNB-1991-46b-1349.pdf 
 Identifier    ZNB-1991-46b-1349 
 Volume    46 
2Author    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