Preparation and C-Si reductive elimination behavior of cis-alkynyl(silyl)platinum(II) complexes

Article abstract of DOI:10.1021/om0302701

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-NCC ₆H₄; 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(O) 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.