A Series of Dinuclear Homo- and Heterometallic Complexes with Two or Three Bridging Sulfido Ligands Derived from the Tungsten Tris (sulfido) Complex [Et4N][(Me2Tp)WS3] (Me2Tp = 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 [Et4N][(Me2Tp)WS3] (1; Me2Tp = hydridotris(3,5-dimethylpyrazol-1-yl)borate) and organometallic precursors is reported. Treatment of 1 with stoichiometric amounts of metal complexes such as [M(PPh3)4] (M = Pt, Pd), [(PtMe3)4((mu)3-I)4], [M(cod)(PPh3)2] [PF6] (M = Ir, Rh; cod = 1,5-cyclooctadiene), [Rh(cod)(dppe)][PF6] (dppe = Ph2PCH2CH2PPh2), [Cp*Ir(MeCN)3][PF6]2 (Cp* = (eta)^5C5Me5), [Cp*Ru(MeCN)3][PF6], and [M(CO)3(MeCN)3] (M = Mo, W) in MeCN or MeCN-THF at room temperature afforded either the doubly bridged complexes [Et4N][(Me2Tp)W(=S)((mu)-S)2M(PPh3)] (M = Pt (3), Pd (4)), [(Me2Tp)W(=S)( (mu)-S)2M(cod)] (M = Ir, Rh (7)), [(Me2Tp)W(=S)( -S)2Rh(dppe)], [(Me2Tp)W(=S)( (mu)-S)2RuCp*] (10), and [Et4N][(Me2Tp)W(=S)( -S)2W(CO)3] (12) or the triply bridged complexes including [(Me2Tp)W((mu)-S)3PtMe3] (5), [(Me2Tp)W((mu)-S)3IrCp*][PF6] (9), and [Et4N][(Me2Tp)W((mu)-S)3Mo (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.