Development of the rational synthetic routes towards trinuclear and cubane-type tetranuclear mixed-metal sulfido clusters containing noble metals

Dimolybdenum and ditungsten complexes containing terminal and bridging sulf ido ligands [M2S2 (mu (2)-S)(2) (S2CNEt2)(2)] (M = Mo, W) react with a rang e of noble-metal complexes to afford a series of trinuclear and cubane-type tetranuclear mixed-metal clusters, whereby the core structure of the produ ced clusters, which is either [M'(mu (2)-S)(2)M-2(mu (2)-S)(2)], [M'(mu (3) -S) (mu (2)-S)(3)M-2], or [M'M-2(2)(mu (3)-S)(4)](M' =Pd, Pt, Rh, Ir, or Ru ), sharply depends upon the choice of the combination M/M' as well as the n ature of the ligands bound to the noble metal incorporated into the cluster . Detailed structures of the new clusters obtained in this study have been determined by the single-crystal X-ray analyses for [Pt(PPh3)(mu (2)-S)(2) {W(S2CNEt2)}(2)(mu (2)-S)(2)], [{Pd(PPh3)}(2){Mo(S2CNEt2)}(2)(mu (3)-S)(4)] , [Ir(PPh3)(2)(mu (3)-S)(mu (2)-S)(3){W(S-2 CNEt2)}(2)(mu (2)-Cl)], [{Rh (c od)}(2) {MOCl(S2CNEt2)}(2)(mu (3)-S)(4)], (cod = 1,5-cyclooctadiene), and [ (CP*Ru)(2){MOCl(S2CNEt2)}(2)(mu (3)-S)(4)] (Cp* = eta (5)-C5Me5).