Borane to Boryl Hydride to Borylene Dihydride: Explicit Demonstration of Boron-to-Metal 伪-Hydride Migration in Aminoborane Activation

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• 作者：Michael O鈥橬eill ; David A. Addy ; Ian Riddlestone ; Michael Kelly ; Nicholas Phillips ; Simon Aldridge
• 刊名：Journal of the American Chemical Society
• 出版年：2011
• 出版时间：August 3, 2011
• 年：2011
• 卷：133
• 期：30
• 页码：11500-11503
• 全文大小：738K
• 年卷期：v.133,no.30(August 3, 2011)
• ISSN：1520-5126

文摘

The sequence of fundamental steps implicit in the conversion of a dihydroborane to a metal borylene complex have been elucidated for an [Ir(PMe₃)₃] system. B鈥揌 oxidative addition has been applied for the first time to an aminodihydroborane, H₂BNR₂, leading to the generation of a rare example of a primary boryl complex, L_n(H)M{B(H)NR₂}; subsequent conversion to a borylene dihydride proceeds via a novel B-to-M 伪-hydride migration. The latter step is unprecedented for group 13 ligand systems, and is remarkable in offering 伪- substituent migration from a Lewis acidic center as a route to a two-coordinate ligand system.