| | 1 | Author
| Dieter Sellmann+, W. Olfgang Kern, Adelgunde Holzmeier, Georg Pöhlmann, M. Atthias, Moll | Requires 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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| ZNB-1991-46b-1349 | | | | Volume
| 46 | |
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