A Stable Homoleptic Divinyl Tetrelene Series

Chemistry. 2021 Jun 10;27(33):8572-8579. doi: 10.1002/chem.202100969. Epub 2021 May 14.

Abstract

The synthesis of the new bulky vinyllithium reagent (Me IPr=CH)Li, (Me IPr=[(MeCNDipp)2 C]; Dipp=2,6-iPr2 C6 H3 ) 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 SiII precursor Me IPr⋅SiBr2 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 SiII 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 (Cp2 Co).

Keywords: ligand design; main group; silylene; tetrelene; vinyl.