The Simplest Amino-borane H2B=NH2 Trapped on a Rhodium Dimer: Pre-Catalysts for Amine-Borane Dehydropolymerization

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• 作者：Amit Kumar ; Nicholas A. Beattie ; Dr. Sebastian D. Pike ; Prof. Stuart A. Macgregor and Prof. Andrew S. Weller
• 刊名：Angewandte Chemie International Edition
• 出版年：2016
• 出版时间：June 1, 2016
• 年：2016
• 卷：55
• 期：23
• 页码：6651-6656
• 全文大小：1949K
• ISSN：1521-3773

文摘

The μ-amino–borane complexes [Rh₂(L^R)₂(μ-H)(μ-H₂B=NHR′)][BAr^F₄] (L^R=R₂P(CH₂)₃PR₂; R=Ph, ⁱPr; R′=H, Me) form by addition of H₃B⋅NMeR′H₂ to [Rh(L^R)(η⁶-C₆H₅F)][BAr^F₄]. DFT calculations demonstrate that the amino–borane interacts with the Rh centers through strong Rh-H and Rh-B interactions. Mechanistic investigations show that these dimers can form by a boronium-mediated route, and are pre-catalysts for amine-borane dehydropolymerization, suggesting a possible role for bimetallic motifs in catalysis.