Thiolate Ligand Transfer from Metallothiolates to Phosphido-Bridged Heterobimetallic Compounds: C−S Bond Cleavage in Benzenethiol and Formation of a Mixed-Metal Trinuclear Compound

Thiolate ligand transfer occurred during the reaction between CpMo(CO) 3 SPh and ( 1 ) in dichloromethane at reflux, resulting in the new mixed-metal and mixed-ligand bridged compound ( 2 ). However, when CpW(CO) 3 SPh reacted with 1 under similar conditions, 2 and the mixed-metal trinuclear compound ( 4 ) were formed. The presence of the (μ-S) 2 bridges in 4 indicates C−S bond cleavage in the SPh ligand. Reflux of a dichloromethane solution of 1 and PhSH also produced 2 along with ( 3 ) and ( 5 ). Moreover, the same reactants in benzene at reflux gave 2, 3, 5, and the additional product ( 6 ). The reaction of 1 with Ph 2 S 2 in dichloromethane at reflux produced compounds 2 and 3. Similarly conducted reactions in benzene at reflux afforded 2, 3, and 6 . Compounds 2 − 6 were characterized by single-crystal X-ray diffraction analyses. Formation of the PPh 3 ligand, which coordinated to 6, suggests C−S bond cleavage in PhSH and Ph 2 S 2. Compounds 3, 5, and 6 were also synthesized in high yield by refluxing 2 with PhSH or Ph 2 S 2, PPh 2 H, and PPh 3, respectively, in benzene.