Roy Matthew M D, Baird Samuel R, Dornsiepen Eike, Paul Lucas A, Miao Linkun, Ferguson Michael J, Zhou Yuqiao, Siewert Inke, Rivard Eric
Department of Chemistry, University of Alberta, 11227 Saskatchewan Dr., Edmonton, Alberta, T6G 2G2, Canada.
Universität Göttingen, Institut für Anorganische Chemie, Tammannstr. 4, 37077, Göttingen, Germany.
Chemistry. 2021 Jun 10;27(33):8572-8579. doi: 10.1002/chem.202100969. Epub 2021 May 14.
The synthesis of the new bulky vinyllithium reagent ( IPr=CH)Li, ( IPr=[(MeCNDipp) C]; Dipp=2,6-iPr C H ) is reported. This vinyllithium precursor was found to act as a general source of the anionic 2σ, 2π-electron donor ligand [ IPr=CH] . Furthermore, a high-yielding route to the degradation-resistant Si precursor IPr⋅SiBr is presented. The efficacy of ( IPr=CH)Li in synthesis was demonstrated by the generation of a complete inorganic divinyltetrelene series ( IPrCH) E: (E=Si to Pb). ( IPrCH) Si: represents the first two-coordinate acyclic silylene not bound by heteroatom donors, with dual electrophilic and nucleophilic character at the Si 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 Co).
报道了新型大位阻乙烯基锂试剂(IPr=CH)Li（IPr = [(MeCNDipp)C]；Dipp = 2,6-iPr₂C₆H₃）的合成。发现这种乙烯基锂前体可作为阴离子型2σ，2π电子给体配体[IPr=CH]⁻的通用来源。此外，还介绍了一条高产率合成抗降解硅前体IPr⋅SiBr₃的路线。通过生成完整的无机二乙烯基四价元素系列(IPrCH)₂E（E = Si至Pb）证明了(IPr=CH)Li在合成中的有效性。(IPrCH)₂Si：代表第一个未被杂原子给体束缚的二配位无环硅烯，其硅中心具有亲电和亲核双重性质。循环伏安法表明这种富电子硅烯是一种强还原剂，其还原能力可与19电子配合物二茂钴（Cp₂Co）相媲美。
