S FUKUZUMI, M FUJITA, J OTERA, Y FUJITA
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 114(26) 10271-10278 1992年12月
Kinetic studies on photoinduced and thermal electron-transfer oxidation of a variety of organosilanes in acetonitrile at 298 K are reported in terms of the electron-transfer rate constants (k(et)) with a series of oxidants having the known one-electron reduction potentials (E0red). The Rehm-Weller Gibbs energy relationship is applied to determine the fundamental parameters for the electron-transfer oxidation, i.e., the one-electron oxidation potentials (E0ox) and the intrinsic barrier for the electron-transfer oxidation (DELTAG(double dagger)0). The E0ox and DELTAG(double dagger)0 values thus obtained are compared with the calculated values of the adiabatic ionization potentials (I(a)) and the inner-sphere reorganization energies (lambda(i)) associated with the structural change upon electron-transfer oxidation by using the PM3 molecular orbital method. Ketene silyl acetals, especially hindered ones, are shown to act as unique and strong electron donors as compared to other organosilanes. On the other hand, Lewis acids such as SnCl4, Ph3SiClO4, and Et3SiClO4, which catalyze the addition of hindered ketene acetals to alpha-enones, are shown to act as strong electron acceptors in the electron-transfer oxidation of ferrooene derivatives. The mechanistic insight to the clectron-transfer oxidation of organosilanes, particularly in the case of hindered ketene silyl acetals which are employed in Lewis acid promoted carbon-carbon bond formation reactions, is discussed on the basis of the fundamental parameters for the electron-transfer oxidation.