A Stable Homoleptic Divinyl Tetrelene Series

The synthesis of the new bulky vinyllithium reagent ((Me)IPr=CH)Li, ((Me)IPr=[(MeCNDipp)(2)C]; Dipp=2,6‐iPr(2)C(6)H(3)) is reported. This vinyllithium precursor was found to act as a general source of the anionic 2σ, 2π‐electron donor ligand [(Me)IPr=CH](−). Furthermore, a high‐yielding route to the degradation‐resistant Si(II) precursor (Me)IPr⋅SiBr(2) is presented. The efficacy of ((Me)IPr=CH)Li in synthesis was demonstrated by the generation of a complete inorganic divinyltetrelene series ((Me)IPrCH)(2)E: (E=Si to Pb). ((Me)IPrCH)(2)Si: represents the first two‐coordinate acyclic silylene not bound by heteroatom donors, with dual electrophilic and nucleophilic character at the Si(II) center noted. Cyclic voltammetry shows this electron‐rich silylene to be a potent reducing agent, rivalling the reducing power of the 19‐electron complex cobaltocene (Cp(2)Co).