Single-Electron Transfer Reactions in Frustrated and Conventional Silylium Ion/Phosphane Lewis Pairs

Silylium ions undergo a single-electron reduction with phosphanes, leading to transient silyl radicals and the corresponding stable phosphoniumyl radical cations. As supported by DFT calculations, phosphanes with electron-rich 2,6-disubstituted aryl groups are sufficiently strong reductants to facilitate this single-electron transfer (SET). Frustration as found in kinetically stabilized triarylsilylium ion/phosphane Lewis pairs is not essential, and silylphosphonium ions, which are generated by conventional Lewis adduct formation of solvent-stabilized trialkylsilylium ions and phosphanes, engage in the same radical mechanism. The trityl cation, a Lewis acid with a higher electron affinity, even oxidizes trialkylphosphanes, such as tBu₃ P, which does not react with either B(C₆ F₅ )₃ or silylium ions.