Synthesis and structure of heterobimetallic compounds with a single thiolato-bridged ligand

Reactions between CpFe(CO)(2)SPh and M(CO)(5)THF (M = Cr, Me, and W) in a m ixture of benzene and THF at room temperature afforded compounds of the typ e CpFe(CO)(2)(mu SPh)M(CO)(5) (1) [M = Cr (1a), Mo (1b), and W (1c)] in hig h yield. However, migration of the thiolato ligand occurred during reaction s between CpM(CO)(x)SPh (M = Fe, x = 2; M = Mo and W, x = 3) and Fe-2(CO)(9 ) forming compounds [Fe(mu SPh)(CO)(3)](2) and [CpM(CO)(x)](2) (M = Fe, x = 2; M = Mo and W, x = 3). Single-crystal X-ray diffraction analyses reveal that 1c is a single thiolato-bridged hererobimetallic compound without a me tal-metal bond, Metal-metal bond formation in compounds 1 by decarbonylatio n under thermal or photolytic condition was not observed. Reactions between compounds 1 and PPh3 produced CpFe(CO)(2)SPh and PPh3M(CO)(5) (M = Cr, Me, and W) by M-S bond cleavage in 1.