Abstract
A series of cis-alkynyl(silyl)platinum(II) complexes, cis-Pt(C⋮CAr)(SiAr‘3)(PMe2Ph)2 (2: Ar = Ph, 4-MeOC6H4, 4-MeC6H4, 4-ClC6H4, 4-BrC6H4, 4-NCC6H4; Ar‘ = Ph, 4-MeOC6H4, 4-MeC6H4, 4-CF3C6H4), have been prepared, and their thermolysis reactions in solution have been examined. Complexes 2 smoothly undergo C−Si reductive elimination in benzene-d6 at around 35 °C to give the corresponding platinum(0) complexes coordinated with silylacetylenes, Pt(ArC⋮CSiAr‘3)(PMe2Ph)2 (3). Kinetic examinations suggest a concerted reaction process that is operative directly from the four-coordinate complexes. The more electron-donating substituents on the Ar and Ar‘ groups provide higher reductive elimination rates.
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