Abstract
The kinetic behavior of dimethyl-, diphenyl-, and dimesitylsilylene in hexanes solution in the presence of methanol (MeOH), tert-butanol (t-BuOH), and the respective O-deuterated isotopomers has been studied, with the goal of elucidating a detailed mechanism for the formal O−H insertion reaction of transient silylenes with alcohols in solution. The data are in all cases consistent with a mechanism involving the intermediacy of the corresponding silylene−alcohol Lewis acid−base complexes, which have been detected directly for each of the SiMe2−ROL and SiPh2−ROL (L = H or D) systems that were studied. Complexation proceeds effectively irreversibly (Keq ≥ 2 × 105 M−1) and at close to the diffusion-controlled rate in these cases. In contrast, the kinetic and spectroscopic behavior observed for SiMes2 in the presence of these alcohols indicates the SiMes2−ROL complexes are involved as steady-state intermediates, formed reversibly and 10−100 times more slowly than is the case with SiMe2 and SiPh2. Product forma...
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