Computational Mechanistic Study of the Hydrogenation and Dehydrogenation Reactions Catalyzed by Cobalt Pincer Complexes
文献类型：期刊论文
| 作者 | Jing, Yuanyuan1; Chen, Xiangyang1,2; Yang, Xinzheng1 |
| 刊名 | ORGANOMETALLICS
 |
| 出版日期 | 2015-12-28 |
| 卷号 | 34期号:24页码:5716-5722 |
| 英文摘要 | The mechanisms of hydrogenation and dehydrogenation reactions catalyzed by a series of aliphatic PNP cobalt pincer complexes, [(PNRPiPr)CoH](+) (R = H and CH2X; X = H, Me, NH2, OMe, OH, F, and CO and [(PNPiPr)CoH], are studied by density functional theory calculations. In the hydrogenation of propylene catalyzed by [(PNPiPr)CoH], a propylene molecule first inserts into the Co-H bond to form a Co-C bond. Then a H-2 molecule is inserted into the Co-C bond for the formation and release of propane. The influence of different substituents on the N atom of the pincer ligand for the hydrogenation process is investigated. The relations between the field/inductive effect (sigma(F)) and total free energy barriers and the properties of the lowest energy intermediates, including the Co-N bond lengths, the lowest unoccupied molecular orbital energies, and the Wiberg bond indices of Co-N bonds, are analyzed. The results show that sigma(F) plays a crucial role in the substituent effect. The mechanism of acceptorless dehydrogenation of alcohols is also elucidated with a detailed free energy profile for the whole catalytic cycle. We found that the very low catalytic activity of [(PNPiPr)CoH] is caused by the easily transfer of H from cobalt to nitrogen to form stable intermediates. |
| 收录类别 | SCI |
| 语种 | 英语 |
| 公开日期 | 2016-03-15 |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/29715]  |
| 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.Univ Chinese Acad Sci, Beijing 100049, Peoples R China |
| 推荐引用方式 GB/T 7714 | Jing, Yuanyuan,Chen, Xiangyang,Yang, Xinzheng. Computational Mechanistic Study of the Hydrogenation and Dehydrogenation Reactions Catalyzed by Cobalt Pincer Complexes[J]. ORGANOMETALLICS,2015,34(24):5716-5722. |
| APA | Jing, Yuanyuan,Chen, Xiangyang,&Yang, Xinzheng.(2015).Computational Mechanistic Study of the Hydrogenation and Dehydrogenation Reactions Catalyzed by Cobalt Pincer Complexes.ORGANOMETALLICS,34(24),5716-5722. |
| MLA | Jing, Yuanyuan,et al."Computational Mechanistic Study of the Hydrogenation and Dehydrogenation Reactions Catalyzed by Cobalt Pincer Complexes".ORGANOMETALLICS 34.24(2015):5716-5722. |
入库方式： OAI收割
来源：化学研究所
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