Tüchler Michael, Gärtner Lisa, Fischer Susanne, Boese A Daniel, Belaj Ferdinand, Mösch-Zanetti Nadia C
Institute of Chemistry, Inorganic Chemistry, University of Graz, Schubertstrasse 1, 8010, Graz, Austria.
Institute of Chemistry, Physical and Theoretical Chemistry, University of Graz, Heinrichstrasse 28, 8010, Graz, Austria.
Angew Chem Int Ed Engl. 2018 Jun 4;57(23):6906-6909. doi: 10.1002/anie.201801800. Epub 2018 May 2.
The terminal zinc hydride complex [Tntm]ZnH (2; Tntm=tris(6-tert-butyl-3-thiopyridazinyl)methanide) is an efficient hydrosilylation catalyst of CO at room temperature without the need of Lewis acidic additives. The inherent electrophilicity of the system leads to selective formation of the monosilylated product (MeO) SiO CH (at room temperature with a TOF of 22.2 h and at 45 °C with a TOF of 66.7 h ). In absence of silanes, the intermediate formate complex [Tntm]Zn(O CH) (3) is quantitatively formed within 5 min. All complexes were fully characterized by H and C NMR spectroscopy and single-crystal X-ray diffraction analyses. Density functional theory (DFT) calculations reveal a high positive charge on zinc and the increased preference of the ligand to adopt a κ -coordination mode.
末端氢化锌配合物[Tntm]ZnH（2；Tntm = 三（6-叔丁基-3-硫代哒嗪基）甲烷化物）是一种在室温下无需路易斯酸性添加剂即可高效催化CO进行硅氢化反应的催化剂。该体系固有的亲电性导致选择性形成单硅烷化产物（MeO）SiO CH（室温下TOF为22.2 h，45℃时TOF为66.7 h）。在没有硅烷的情况下，中间体甲酸配合物[Tntm]Zn（O CH）（3）在5分钟内定量形成。所有配合物均通过1H和13C NMR光谱以及单晶X射线衍射分析进行了全面表征。密度泛函理论（DFT）计算表明锌上具有高正电荷，并且配体更倾向于采用κ-配位模式。
