Mechanisms of the transfer hydroformylation catalyzed by rhodium, cobalt, and iridium complexes: Insights from density functional theory study
文献类型：期刊论文
| 作者 | Dong, Chunhua1,2,3; Ji, Mingsong1; Yang, Xinzheng1; Yao, Jiannian2; Chen, Hui2 |
| 刊名 | JOURNAL OF ORGANOMETALLIC CHEMISTRY
 |
| 出版日期 | 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 |
| 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 |
| 推荐引用方式 GB/T 7714 | 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. |
入库方式： OAI收割
来源：化学研究所
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