A series of dinuclear homo- and heterometallic complexes with two or three bridging sulfido ligands derived from the tungsten tris(sulfido) complex [Et(4)N][(Me(2)Tp)WS(3)] (Me(2)Tp = hydridotris(3,5-dimethylpyrazol-1-yl)borate)

The generation of heterobimetallic complexes with two or three bridging sulfido ligands from mononuclear tris(sulfido) complex of tungsten Et(4)N](Me(2)Tp)WS(3)] (1; Me(2)Tp = hydridotris(3,5-dimethylpyrazol-1-yl)borate) and organometallic precursors is reported. Treatment of 1 with stoichiometric amounts of metal complexes such as M(PPh(3))(4)] (M = Pt, Pd), (PtMe(3))(4)(micro(3)-I)(4)], M(cod)(PPh(3))(2)]PF(6)] (M = Ir, Rh; cod = 1,5-cyclooctadiene), Rh(cod)(dppe)]PF(6)] (dppe = Ph(2)PCH(2)CH(2)PPh(2)), CpIr(MeCN)(3)]PF(6)](2) (Cp = eta(5)-C(5)Me(5)), CpRu(MeCN)(3)]PF(6)], and M(CO)(3)(MeCN)(3)] (M = Mo, W) in MeCN or MeCN-THF at room temperature afforded either the doubly bridged complexes Et(4)N](Me(2)Tp)W(=S)(micro-S)(2)M(PPh(3))] (M = Pt (3), Pd (4)), (Me(2)Tp)W(=S)(micro-S)(2)M(cod)] (M = Ir, Rh (7)), (Me(2)Tp)W(=S)(micro-S)(2)Rh(dppe)], (Me(2)Tp)W(=S)(micro-S)(2)RuCp] (10), and Et(4)N](Me(2)Tp)W(=S)(micro-S)(2)W(CO)(3)] (12) or the triply bridged complexes including (Me(2)Tp)W(micro-S)(3)PtMe(3)] (5), (Me(2)Tp)W(micro-S)(3)IrCp]PF(6)] (9), and Et(4)N](Me(2)Tp)W(micro-S)(3)Mo(CO)(3)] (11), depending on the nature of the incorporated metal fragment. The X-ray analyses have been undertaken to clarify the detailed structures of 3-5, 7, and 9-12.