Synthesis and characterization of heterobimetallic complexes containing C-S cleaved thiophenes

The insertion of the 16e frspments 1( triphos)MH 1 into ;1C -S bond in thiophen*c, 23'~bithiophene or henzolbjthiophene gives butadienethiolute or 2 -vinylthiophenol;tte complexes in which the sulfur utom becomes a powerful nucieophile (M =Rh. Ir: triphos =MeCtCH,PPh:),). This sulfur iitom is uttucked by unsuturrted M'(C0)5 fragments (M' =Cr, Mo, W). As a result, heterobimetallic complexes are obtained in which the C-S inserted thiophene bridges the two metul centres via the sulfur atom. The strength of the M'-S bonding intcrikxion increases in the order MO 4 Cr < W. All the compoundsw ere chuructcrizedin solution by multinuclear NMR spectroscopy.