Polar X-H Bond (X=O, S, N) Activation at a Cage Silanide.

Low-valent silicon compounds such as neutral silylenes display versatile reactivity for the activation of small molecules. In contrast, their anionic congeners silanides ([R 3 Si - ]) have primarily been investigated for their nucleophilic reactivity. Here we show that incorporating a silanide center in a bicyclic cage structure allows for formal oxidative addition of polar element-hydrogen bonds (RX-H, R=aromatic residue, X=O, S, NH). The resulting hydrosilicates were isolated and characterized structurally and spectroscopically. Density Functional Theory (DFT) calculations and experimental observations support an ionic mechanism for RX-H bond activation. Finally, the reactivity of the RS-H bond adduct was further investigated, revealing that it behaves as a Lewis pair upon facile heterolytic cleavage of the Si-S bond.