亚锗烯：一种多功能低价态第14族催化剂。
Germyliumylidene: A Versatile Low Valent Group 14 Catalyst.
作者信息
Sarkar Debotra, Dutta Sayan, Weetman Catherine, Schubert Emeric, Koley Debasis, Inoue Shigeyoshi
机构信息
Department of Chemistry, WACKER-Institute of Silicon Chemistry and Catalysis Research Center, Technische Universität München, Lichtenbergstraße 4, 85748, Garching, Germany.
Department of Chemical Sciences, Indian Institute of Science Education and Research (IISER) Kolkata, Mohanpur, 741 246, India.
出版信息
Chemistry. 2021 Sep 9;27(51):13072-13078. doi: 10.1002/chem.202102233. Epub 2021 Jul 29.
Bis-NHC stabilized germyliumylidenes [RGe(NHC) ] are typically Lewis basic (LB) in nature, owing to their lone pair and coordination of two NHCs to the vacant p-orbitals of the germanium center. However, they can also show Lewis acidity (LA) via Ge-C σ* orbital. Utilizing this unique electronic feature, we report the first example of bis-NHC-stabilized germyliumylidene [ TerGe(NHC) ]Cl (1), ( Ter=2,6-(2,4,6-Me C H ) C H ; NHC= IMe =1,3,4,5-tetramethylimidazol-2-ylidene) catalyzed reduction of CO with amines and arylsilane, which proceeds via its Lewis basic nature. In contrast, the Lewis acid nature of 1 is utilized in the catalyzed hydroboration and cyanosilylation of carbonyls, thus highlighting the versatile ambiphilic nature of bis-NHC stabilized germyliumylidenes.
双-NHC稳定的锗亚烷基[RGe(NHC)]本质上通常是路易斯碱（LB），这归因于它们的孤对电子以及两个NHC与锗中心的空p轨道的配位。然而，它们也可以通过Ge-C σ*轨道表现出路易斯酸性（LA）。利用这种独特的电子特性，我们报道了双-NHC稳定的锗亚烷基[TerGe(NHC)]Cl（1）（Ter = 2,6-(2,4,6-Me₃C₆H₂)₂C₆H₃；NHC = IMe = 1,3,4,5-四甲基咪唑-2-亚基）催化胺和芳基硅烷还原CO的首个实例，该反应通过其路易斯碱性质进行。相比之下，1的路易斯酸性质用于羰基的催化硼氢化和氰基硅烷化反应，从而突出了双-NHC稳定的锗亚烷基的多功能两性性质。
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