Cabrera-Trujillo Jorge Juan, Fernández Israel
Departamento de Química Orgánica I and Centro de Innovación en Química Avanzada (ORFEO-CINQA), Facultad de Ciencias Químicas, Universidad Complutense de Madrid, 28040 Madrid, Spain.
Dalton Trans. 2020 Mar 14;49(10):3129-3137. doi: 10.1039/c9dt04806e. Epub 2020 Feb 19.
The role of frustrated Lewis pairs (FLPs) as ligands in gold(i) catalyzed-reactions has been computationally investigated by using state-of-the-art density functional theory calculations. To this end, the nature of (P,B)-FLP-transition metal interactions in different gold(i)-complexes has been first explored in detail with the help of the energy decomposition analysis method, which allowed us to accurately quantify the so far poorly understood AuB interactions present in these species. The impact of such interactions on the catalytic activity of gold(i)-complexes has been then evaluated by performing the Au(i)-catalyzed hydroarylation reaction of phenylacetylene with mesitylene. With the help of the activation strain model of reactivity, the factors governing the higher activity of Au(i)-complexes having a FLP as a ligand as compared to that of the parent PPh system have also been quantitatively identified.
通过使用最先进的密度泛函理论计算，对受挫路易斯对（FLP）作为配体在金（I）催化反应中的作用进行了计算研究。为此，首先借助能量分解分析方法详细探索了不同金（I）配合物中（磷，硼）-FLP-过渡金属相互作用的本质，这使我们能够准确量化这些物种中迄今了解甚少的金硼相互作用。然后通过进行苯乙炔与均三甲苯的金（I）催化氢芳基化反应，评估了这种相互作用对金（I）配合物催化活性的影响。借助反应性的活化应变模型，还定量确定了与母体PPh体系相比，具有FLP作为配体的金（I）配合物具有更高活性的控制因素。
