Dalla Tiezza Marco, Bickelhaupt F Matthias, Orian Laura
Dipartimento di Scienze Chimiche, Università degli Studi di Padova, Via Marzolo 1, 35129, Padova, Italy.
Department of Theoretical Chemistry and Amsterdam Center for Multiscale Modeling (ACMM), Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV, Amsterdam, The Netherlands.
Chemphyschem. 2018 Jul 17;19(14):1766-1773. doi: 10.1002/cphc.201800178. Epub 2018 May 2.
The intramolecular oxidative coupling converting a bis-acetylene complex of formula CpM (C H ) (Cp=C H ; M=Co, Rh, Ir) into a 16-electron metallacycle is studied in silico. This reaction is paradigmatic in acetylene [2+2+2] cycloaddition to benzene catalyzed by CpM fragments, being the step with the highest activation energy, and thus affecting the whole catalysis. Our activation strain and quantitative molecular orbital (MO) analyses elucidate the mechanistic details and reveal why cobalt performs better than rhodium and iridium catalysts outlining general principles for rational design of catalysts to be used in these processes.
在计算机模拟中研究了将式为CpM(C₂H₂)₂（Cp = C₅H₅；M = Co、Rh、Ir）的双乙炔配合物转化为16电子金属环的分子内氧化偶联反应。该反应是由CpM片段催化的乙炔与苯的[2+2+2]环加成反应中的典型反应，是具有最高活化能的步骤，因此影响整个催化过程。我们的活化应变和定量分子轨道（MO）分析阐明了机理细节，并揭示了钴比铑和铱催化剂表现更好的原因，勾勒出了用于这些过程的催化剂合理设计的一般原则。
