Reactions of α,β-Unsaturated Thioesters with Platinum(0): Implication of a Dual Mechanism Leading to the Formation of Acyl Platinum

The moderate reactivity of the α,β-unsaturated thioester (ArS)C(O)C( A ) C( B )(H) toward Pt(PPh 3 ) 2 (C 2 H 4 ) has been used to extract thermodynamic and kinetic information pertaining to the oxidative addition of α,β-unsaturated acid halide derivatives to low-valent transition-metal complexes. The results indicate acyl platinum product complexes can form by direct C−S bond cleavage or by attack of coordinated Pt(PPh 3 ) 2 on the β-carbon.