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

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. Double silyl transfer: Pyrazine‐based reductants capable of transferring two electrons and two silyl groups have been demonstrated to effectively functionalize various unsaturated organic moieties as well as deoxygenate a number of main group oxides. Solvent appears to play a significant role in facilitating these reductive transformations allowing for reactivity under mild conditions with high conversion.