石油化工2025，Vol.54Issue(9)：1248-1256,9.DOI:10.3969/j.issn.1000-8144.2025.09.004
Co络合物催化C≡C键选择性氢化的机理研究
Mechanistic insights into selective hydrogenation of C≡C bonds catalyzed by cobalt complexes
郑文玉1
作者信息
- 1. 中石化(北京)化工研究院有限公司,北京 100013
- 折叠
摘要
Abstract
The reaction mechanism of diphenylacetylene semi-hydrogenation to(E)-1,2-diphenylethylene catalyzed by(MesCCC)Co(H2)(PPh3)(MesCCC:bis(mesityl-benzimidazol-2-ylidene)phenyl;PPh3:triphenylphosphine)complexes was investigated by density functional theory.The results reveal that the cobalt dihydrogen complex(MesCCC)Co(H2)and its less stable dihydride isomer(MesCCC)Co(H)2 form a catalytic system.This means(MesCCC)Co(H)2 first catalyzes the semi-hydrogenation of alkynes to(Z)-1,2-diphenylethylene,followed by the isomerization of the Z-alkene to(E)-1,2-diphenylethene mediated by(MesCCC)Co(H2).Additionally,the free energy barrier for(MesCCC)Co complexes to catalyze the isomerization of E-olefin to Z-olefin is so high that this process is difficult to progress,which is the root cause of the high E-selectivity of the reaction.This study elucidates the reaction mechanism of(MesCCC)Co complexes catalyzing semi-hydrogenation of alkynes to E-olefin and proposes a molecular design scheme to improve the catalytic performance of the catalyst.关键词
钴络合物/炔烃/氢化/半氢化/选择性Key words
cobalt complex/alkyne/hydrogenation/semi-hydrogenation/selectivity分类
化学化工引用本文复制引用
郑文玉..Co络合物催化C≡C键选择性氢化的机理研究[J].石油化工,2025,54(9):1248-1256,9.
