Non-Covalent Interactions Drive the Efficiency of Molybdenum Imido Alkylidene Catalysts for Olefin Metathesis,Journal of the American Chemical Society

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Non-Covalent Interactions Drive the Efficiency of Molybdenum Imido Alkylidene Catalysts for Olefin Metathesis
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2019-06-10 , DOI: 10.1021/jacs.9b04367
Marco A B Ferreira _{1,

2} , Jordan De Jesus Silva ₃ , Samantha Grosslight ₁ , Alexey Fedorov _{3,

4} , Matthew S Sigman ₁ , Christophe Copéret ₃

Affiliation

High-throughput experimentation and multivariate modelling allow identification of non-covalent interactions (NCIs) in monoaryloxy-pyrrolide Mo imido alkylidene metathesis catalysts prepared in situ as a key driver for high activity in a representative crossmetathesis reaction (homodimerization of 1-nonene). Statistical univariate and multivariate modelling categorizes catalytic data from 35 phenolic ligands into two groups, depending on the substitution in the ortho position of the phenol ligand. Catalytic activity descriptor TON1h correlates predominantly with attractive NCIs when ortho aryl phenols are used and, conversely, with repulsive NCIs when the phenol has no aryl ortho substituents. Energetic span analysis is deployed to relate the observed NCI and the cycloreversion metathesis step such that aryloxide ligands with no ortho aryls mainly impact the energy of metallacyclobutane intermediates (SP/TBP isomers), whereas aryloxides with pendant ortho aryls influence the transition state energy for the cycloreversion step. While the electronic effects from the aryloxide ligands also play a role, our work outlines how NCIs may be exploited for the design of improved d0 metathesis catalysts.

中文翻译：

非共价相互作用提高了用于烯烃复分解的钼亚胺亚烷基催化剂的效率

高通量实验和多变量建模允许识别原位制备的单芳氧基-吡咯烷钼亚胺亚烷基复分解催化剂中的非共价相互作用 (NCI)，作为代表性交叉复分解反应（1-壬烯的均二聚化）中高活性的关键驱动因素。统计单变量和多变量建模将来自 35 个酚配体的催化数据分为两组，具体取决于酚配体邻位的取代。当使用邻芳基苯酚时，催化活性描述符 TON1h 主要与有吸引力的 NCI 相关，相反，当苯酚没有芳基邻位取代基时，与排斥 NCI 相关。能量跨度分析用于将观察到的 NCI 和环还原复分解步骤联系起来，这样没有邻芳基的芳基氧化物配体主要影响金属环丁烷中间体（SP/TBP 异构体）的能量，而带有悬垂邻芳基的芳基氧化物影响过渡态能量循环回复步骤。虽然芳基氧化物配体的电子效应也起作用，但我们的工作概述了如何利用 NCI 来设计改进的 d0 复分解催化剂。

更新日期：2019-06-10

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