Mechanistic investigation of the transfer hydrogenation of alkynes catalysed by an MLC catalyst with multiple ancillary ligand sites†

Yuan Zhang , Lan-Yu Li , Cheng Hou
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Abstract

This study reveals the mechanistic details of the transfer hydrogenation catalyzed by an MLC catalyst with multiple ancillary ligand sites.

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具有多个辅助配体位点的MLC催化剂催化炔烃转移加氢的机理研究†
基于辅助配体的均相有机金属催化剂在有机合成中具有重要应用。近年来,在辅助配体中引入多个功能位点代表了金属-配体合作(MLC)催化剂设计的新方向。然而,活性物种中多个功能位点的参与导致了复杂的影响因素和不确定的反应机制。本文进行了一项理论研究,以阐明辅助配体中具有多个官能团的MLC催化剂催化炔烃转移加氢的机理偏好。计算表明,传统的M–L键MLC模式具有较高的活化能垒(34.3 kcal mol−1)。相反,催化剂采用了一种不寻常的MLC模式,其中NEt2基团表现为非无辜配体,并通过更容易获得的活化自由能垒(22.6 kcal mol−1)促进转移氢化。进一步的理论分析表明,NEt2基团的半稳定性增加了Co(i)氢化物配合物在插入反应中的亲核性,并降低了质子转移过程中过渡态的环应变。催化剂的灵活配位模式避免了不利的空间排斥,导致基质从钴中心的活化增强。我们的研究证明了具有多个辅助配体位点的MLC催化剂的机理多样性,预计这将为未来的均相催化剂设计提供灵感。
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