Reductive Silylation Using a Bis‐silylated Diaza‐2,5‐cyclohexadiene

Abstract 1,4‐Bis(trimethylsilyl)‐1,4‐diaza‐2,5‐cyclohexadiene, 1 , was tested as a reagent for the reductive silylation of various unsaturated functionalities, including N‐heterocycles, quinones, and other redox‐active moieties in addition to deoxygenation of main group oxides. Whereas most reactions tested are thermodynamically favorable, based on DFT calculations, a few do not occur, perhaps giving limited insight on the mechanism of this very attractive reductive process. Of note, reductive silylation reactions show a strong solvent dependence where a polar solvent facilitates conversions.