Preparation of mononuclear tungsten tris(sulfido) and molybdenum sulfido-tetrasulfido complexes with hydridotris(pyrazolyl)borate coligand and conversion of the former into sulfido-bridged bimetallic complex having Pt(mu-S)(2)WS core

Treatment of [Et4N] [(Me(2)Tp)W(CO)(3)] (Me(2)Tp = HB(3,5-dimethylpyrazol-1 -yl)(3)) with S-8 in DMF at room temperature afforded a tris(sulfido) compl ex [Et4N][(Me(2)Tp)WS3] (1a), while that of [Et4N][TpW(CO)(3)] (Tp = HB(pyr azol-1-yl)(3)) in MeCN resulted in the formation of [Et4N][TpWS(3)] (1b) al ong with [Et4N](2)[{WO(S-2)(2)}(2)-(mu -S)] (6) as a byproduct. Under simil ar conditions, [Et4N][(Me(2)Tp)Mo(CO)(3)] gave a mixture of a sulfido-tetra sulfido complex [Et4N][(Me(2)Tp)MoS(S-4)] (2a) and its monooxo analogue [Et 4N][(Me(2)Tp)MoO(S-4)], although a sulfido-tetrasulfido complex [Et4N][TpMo S(S-4)] (2b) was exclusively obtained from [E4N][TpMo(CO)(3)]. The reaction of 1a with [PtCl2(cod)] (cod = 1,5-cyclooctadiene) in MeCN at room tempera ture led to the formation of a sulfide-bridged mixed-metal complex [Et4N][( Me(2)Tp)WS(mu -S)(2)PtCl2] (10). The structures of new complexes have been determined in detail by the X-ray analyses for 1a . MeCN, 1b, 2a, 2b, 6, an d 10.