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Since substrate addition and elimination reactions are essential reactions of metal sulfur centres in oxidoreductases, we investigated the substitution of chloride in [Mo(Cl)(NO)(′S 4 ')](1) (′S 4′2-  = 1,2-Bis(2-mercaptophenylthio)ethane(2-)) [4] and in the analogous tungsten complex [W(Cl)(NO)(′S 4 ')](2). The chloride ligands in 1 and 2 can easily be substituted by thiolates to give [M(SR)(NO)(′S 4 ')] (M = Mo, R = Me 3a,′Pr 3b,  n Bu 3c, Ph 3d; M = W, R = Me 4a, Ph 4b). For these substitution reactions an associative mechanism is suggested. The SR -  ligands act probably as σ-π four electron donor ligands to give metal centres with an 18 electron configuration as also found in the amido complexes [Mo(NR 2 )(NO)('S 4 ')] [4]. 1 and 2 react with PMe 3  to yield the adducts [M(PMe 3 )(Cl)(NO)('S 4 ')] (M = Mo 5, W 6), whose NMR spectra indicate the formation of two stereoisomers in a ratio of about 2:3.

zeitschrift für naturforschung b

Übergangsmetallkomplexe mit Schwefelliganden, LXVI / Transition Metal Complexes with Sulfur Ligands, LXVI: Substitutions- und Additionsreaktionen an Molybdän- und Wolfram-Schwefel-Zentren von [M(Cl)(NO)(′S 4 ')], M = Mo, W, mit Thiolaten SR -  (R = Me,  i Pr,  n Bu, Ph) und PMe 3 (′S 4 ' 2-  = 1,2-Bis(2-mercaptophenylthio)ethan(2-)) / Substitution and Addition Reactions at Molybdenum and Tungsten Sulfur Centres of [M(Cl)(NO)(′S 4 ')], M = Mo, W, with Thiolates SR -  (R = Me,  i Pr,  n Bu, Ph) and PMe 3 (′S 4 ' 2-  = 1,2-Bis(2-mercaptophenylthio)ethane(2-))