Binuclear complexes with ligands based on the 2,6-bis(diphenylphosphinomethyl)benzene framework. Syntheses and crystal structures of [Ir2Cl2(mu-CO){2,6-(Ph2PCH2)(2)C6H3S}(2)]center dot 2CH(2)Cl(2), [Ni-2{2.6-(Ph2PCH2)(2)C6H4S}(2)][PF6](2)center dot Et2O center dot 0.5CH(2)Cl(2) and [Rh2Cl2(CO)(2){1,3-(Ph2PCH2)(2)C6H4}(2)]

The new binucleating phosphinothiolate proligand 2,6-(Ph2PCH2)C6H4SH (L3H) was prepared from bromo-2,6-dimethylbenzene in a 4 step synthesis. Reaction with [IrCl(CO)(PPh3)(2)] in MeCN gave the carbonyl and thiolate bridged di mer [Ir2Cl(mu-CO)(L3)(2)] 1. Reaction of [{RhCl(CO)(2)}(2)] with half an eq uivalent of L3H resulted in formation of the dimeric species [Rh2Cl(CO)(2)( L3)] 2 with one bridging thiolate and one bridging chloride. The dimeric sp ecies [Ni-2(L3)(2)](2+) 3 was formed in high yield from reaction of[NiCl2(P Ph3)(2)] with L3H in MeCN. The diphosphine 1,3-(Ph2PCH2)(2)C6H4 (L4) gave t he dimeric species [Rh2Cl2(CO)(2)(L4)(2)] 4 with [RhCl(CO)(PPh3)(2)] with n o evidence for metallation at the bridging aryl group. The crystal structur es of complexes 1, 3 and 4 are discussed.