Cortés Iván, Cabrera-Trujillo Jorge Juan, Fernández Israel
Instituto de Química Rosario (IQUIR, CONICET-UNR), Facultad de Ciencias Bioquímicas y Farmacéuticas and Universidad Nacional de Rosario, Suipacha 531, 2000 Rosario, Argentina.
Departamento de Química Orgánica I y Centro de Innovación en Química Avanzada (ORFEO-CINQA), Facultad de Ciencias Químicas, Universidad Complutense de Madrid, 28040-Madrid, Spain.
Dalton Trans. 2021 Dec 14;50(48):18036-18043. doi: 10.1039/d1dt03721h.
The physical factors behind the experimentally observed high activity of gold(I)-catalysts having an α-cationic phosphole as a ligand have been computationally explored. To this end, the gold(I)-catalysed hydroarylation reactions of phenylacetylene and mesitylene involving both neutral and cationic phosphole as well as phosphine ligands have been quantitatively analyzed in detail with the help of the activation strain model of reactivity in combination with the energy decomposition analysis method. It is found that the cationic phosphole ligands induce a dramatic change in both the geometry and the electronic structure of the initially formed π-complex which significantly enhances its electrophilicity. This results in an enhancement of the key π(mesitylene) → π*(LAu-acetylene complex) molecular orbital interaction which is the main factor responsible for the activating effect of these cationic ligands.
通过计算探索了以α-阳离子膦作为配体的金（I）催化剂在实验中观察到的高活性背后的物理因素。为此，借助反应性的活化应变模型并结合能量分解分析方法，对涉及中性和阳离子膦以及膦配体的苯乙炔和均三甲苯的金（I）催化氢芳基化反应进行了详细的定量分析。研究发现，阳离子膦配体在最初形成的π配合物的几何结构和电子结构上都引起了显著变化，这显著增强了其亲电性。这导致关键的π（均三甲苯）→π*（LAu - 乙炔配合物）分子轨道相互作用增强，这是这些阳离子配体产生活化作用的主要因素。
