Insertion of Cyclic Alkyl(amino) Carbene into the Si–H Bonds of Hydrochlorosilanes

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• 作者：Chandrajeet Mohapatra ; Prinson P. Samuel ; Bin Li ; Benedikt Niepötter ; Christian J. Schürmann ; Regine Herbst-Irmer ; Dietmar Stalke ; Bholanath Maity ; Debasis Koley ; Herbert W. Roesky
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：March 7, 2016
• 年：2016
• 卷：55
• 期：5
• 页码：1953-1955
• 全文大小：232K
• ISSN：1520-510X

文摘

Carbenes are known for their ability to abstract HCl from hydrochlorosilanes to form carbene hydrochloride adducts. In contrast, the Si–H bond insertion products RSiCl₂(cAACH) (2, 4, 6, and 8) have been formed in the reaction of RSiHCl₂ [R = Ar(SiMe₃)N (1), Cp* (3), PhC(NtBu)₂ (5), Cl (7); Ar = 2,6-iPr₂C₆H₃] with a cyclic alkyl(amino) carbene (cAAC:) irrespective of the steric demand of the R group. The new products have been characterized by various analytical tools including X-ray crystallography, electron ionization mass spectrometry, and NMR spectroscopy. Theoretical investigations have also been performed to understand why cAAC prefers insertion into the Si–H bond rather than the dehydrohalogenation pathway.