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Computational prediction on the catalytic activity of heterobimetallic complex featuring MMˊ triple bond in acetylene cyclotrimerization: Mechanistic study
Author(s) -
Zhang Na,
Mi Jinhui,
Huo Suhong,
Meng Lingpeng,
Li Xiaoyan
Publication year - 2021
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.26471
Subject(s) - acetylene , chemistry , triple bond , cycloaddition , catalysis , ring (chemistry) , atom (system on chip) , activation barrier , density functional theory , reaction mechanism , computational chemistry , population , double bond , polymer chemistry , organic chemistry , demography , sociology , computer science , embedded system
Abstract A detailed reaction mechanism of acetylene cyclotrimerization catalyzed by V( i PrNPMe 2 ) 3 Fe‐PMe 3 (denote as CAT), a heterobimetallic complex featuring V‐Fe triple bond, was computationally investigated using density functional theory. The calculated results show that the first acetylene firstly attaches to the V atom of CAT to get a four‐membered ring structure through [2 + 2] cycloaddition reaction. For the second acetylene addition, there are two cyclotrimerization mechanisms, outer sphere mechanism and inner mechanism. The inner sphere reaction pathway is the main reaction pathway. By replacing the V with Nb and Ta, Fe with Ru and Os, a series of new catalysts are screened computationally. The calculated results show that, all of the nine heterobimetallic complexes show high activity at mild condition. The energy barrier of the rate determining step is related to the natural population analysis (NPA) charge of Mˊ and the Wiberg bond index (WBI) of M‐Mˊ bond. The more negative NPA charge of Mˊ and the smaller WBI of M‐Mˊ bond, the lower energy barrier is.