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A Highly Active Bidentate Magnesium Catalyst for Amine‐Borane Dehydrocoupling: Kinetic and Mechanistic Studies

机译:用于胺-硼烷脱氢偶联的高活性双齿镁催化剂:动力学和机理研究

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摘要

A magnesium complex (>1) featuring a bidentate aminopyridinato ligand is a remarkably selective catalyst for the dehydrocoupling of amine‐boranes. This reaction proceeds to completion with low catalyst loadings (1 mol %) under mild conditions (60 °C), exceeding previously reported s‐block systems in terms of selectivity, rate, and turnover number (TON). Mechanistic studies by in situ NMR analysis reveals the reaction to be first order in both catalyst and substrate. A reaction mechanism is proposed to account for these findings, with the high TON of the catalyst attributed to the bidentate nature of the ligand, which allows for reversible deprotonation of the substrate and regeneration of >1 as a stable resting state.
机译:具有二齿氨基吡啶并配体的镁配合物(> 1 )是胺-硼烷脱氢偶联的显着选择性催化剂。该反应在温和的条件下(60 C)以低催化剂负载量(1 mol%)进行完成,在选择性,速率和周转数(TON)方面超过了先前报道的s-block系统。通过原位NMR分析的机理研究表明该反应在催化剂和底物中都是一级反应。提出了一种反应机理来解释这些发现,其中催化剂的高TON归因于配体的双齿性质,这使得底物可逆地去质子化并> 1 的再生作为稳定的静息。州。

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