Nucleophilicity and Electrophilicity in the Gas Phase: Silane Hydricity

Hydricity is of great import as hydride transfer reactions are prominent in many processes, including organic synthesis, photoelectrocatalysis, and hydrogen activation. Herein, the kinetic hydricity of a series of silanes is examined in the gas phase. Most of these reactions have not heretofore been studied in vacuo and provide valuable data that can be compared to condensed-phase hydricity, to reveal the effects of solvent. Both experiments and computations are used to gain insight into mechanism and reactivity. In a broader sense, these studies also represent a first step toward systematically understanding nucleophilicity and electrophilicity in the absence of a solvent.