Matthew M D Roy1, Samuel R Baird1, Eike Dornsiepen1, Lucas A Paul2, Linkun Miao1, Michael J Ferguson1, Yuqiao Zhou1, Inke Siewert3, Eric Rivard4. 1. University of Alberta, Chemistry, 11227 Saskatchewan Drive, T6G 2G2, Edmonton, CANADA. 2. University of Gottingen: Georg-August-Universitat Gottingen, Institut fur Anorganische Chemie, Tammannstr. 4, 37077, Göttingen, GERMANY. 3. University of Göttingen: Georg-August-Universitat Gottingen, Institute fur Anorganische Chemie, Tammannstr. 4, 37077, Göttingen, GERMANY. 4. University of Alberta, Deptm. of Chemistry, 11227 Saskatchewan Dr., T6G 2G2, Edmonton, CANADA.
Abstract
The synthesis of the new bulky vinyllithium reagent (MeIPr=CH)Li, (MeIPr = [(MeCNDipp)2C]; Dipp = 2,6- iPr2C6H3 ) is reported. This vinyllithium precursor was found to act as a general source of the anionic 2σ, 2π-electron donor ligand [MeIPr=CH]- . Furthermore a high-yielding route to the degradation-resistant SiII precursor MePr•SiBr2 is presented. The efficacy of (MeIPr=CH)Li in synthesis was demonstrated by the generation of a complete inorganic divinyltetrelene series (MeIPrCH) 2 E: (E = Si to Pb). (MeIPrCH)2Si: 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 (Cp2Co).
The synthesis of the new bulky n class="Chemical">vinyllithium reagent (MeIPr=CH)Li, (MeIPr = [(MeCNDipp)2C]; Dipp = 2,6- iPr2C6H3 ) is reported. This vinyllithium precursor was found to act as a general source of the anionic 2σ, 2π-electron donor ligand [MeIPr=CH]- . Furthermore a high-yielding route to the degradation-resistant SiII precursor MePr•SiBr2 is presented. The efficacy of (MeIPr=CH)Li in synthesis was demonstrated by the generation of a complete inorganic divinyltetrelene series (MeIPrCH) 2 E: (E = Si to Pb). (MeIPrCH)2Si: 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 (Cp2Co).
Authors: Matthias T Ackermann; Michael Seidl; Fuwei Wen; Michael J Ferguson; Alexey Y Timoshkin; Eric Rivard; Manfred Scheer Journal: Chemistry Date: 2021-11-24 Impact factor: 5.020