Mechanisms of the transfer hydroformylation catalyzed by rhodium, cobalt, and iridium complexes: Insights from density functional theory study
Dong, Chunhua1,2,3; Ji, Mingsong1; Yang, Xinzheng1; Yao, Jiannian2; Chen, Hui2
刊名JOURNAL OF ORGANOMETALLIC CHEMISTRY
2017-03-15
卷号833页码:71-79
关键词Reaction Mechanism Transfer Hydroformylation Homogeneous Catalysis Rhodium Cobalt Iridium
英文摘要The mechanisms of the transfer hydroformylation reactions catalyzed by rhodium, cobalt, and iridium complexes were studied by using the density functional theory. There are nine stages in each catalytic cycle: oxidation addition and C-H activation, hydrogen transfer and benzoic acid dissociation, anti insertion reaction (decarbonylation), beta-H elimination, nucleophilic substitution 1 (S(N)1) of ligand, C=C insertion, C=O insertion, coordination of benzoic acid and hydrogen transfer, and reductive elimination and aldehyde dissociation for catalyst regeneration. The total free energy barriers of the reactions catalyzed by Rh, Co and Ir complexes are 25.1 (3(Rh) -> TS11,12-Rh), 27.3 (1(Co) -> TS5,6-Co) and 41.5 (14(Ir) -> TS14,1-Ir) kcal/mol, respectively. Such barriers indicate that the newly proposed cobalt complex could be a potential low-cost catalyst for the transfer hydroformylation reaction under mild conditions. The electronic structures of key intermediates and transition states in the reactions were analyzed by using the natural bond orbital theory and the Multiwfn program. (C) 2017 Elsevier B.V. All rights reserved.
语种英语
内容类型期刊论文
源URL[http://ir.iccas.ac.cn/handle/121111/38291]  
专题化学研究所_分子动态与稳态结构实验室
作者单位1.Chinese Acad Sci, Inst Chem, State Key Lab Struct Chem Unstable & Stable Speci, Beijing Natl Lab Mol Sci, Beijing 100190, Peoples R China
2.Chinese Acad Sci, Inst Chem, CAS Key Lab Photochem, Beijing Natl Lab Mol Sci, Beijing 100190, Peoples R China
3.Handan Univ, Handan Key Lab Organ Small Mol Mat, Coll Chem Chem Engn & Mat, Handan 056005, Peoples R China
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Dong, Chunhua,Ji, Mingsong,Yang, Xinzheng,et al. Mechanisms of the transfer hydroformylation catalyzed by rhodium, cobalt, and iridium complexes: Insights from density functional theory study[J]. JOURNAL OF ORGANOMETALLIC CHEMISTRY,2017,833:71-79.
APA Dong, Chunhua,Ji, Mingsong,Yang, Xinzheng,Yao, Jiannian,&Chen, Hui.(2017).Mechanisms of the transfer hydroformylation catalyzed by rhodium, cobalt, and iridium complexes: Insights from density functional theory study.JOURNAL OF ORGANOMETALLIC CHEMISTRY,833,71-79.
MLA Dong, Chunhua,et al."Mechanisms of the transfer hydroformylation catalyzed by rhodium, cobalt, and iridium complexes: Insights from density functional theory study".JOURNAL OF ORGANOMETALLIC CHEMISTRY 833(2017):71-79.
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