globalchange  > 气候减缓与适应
DOI: 10.1016/j.jcou.2018.02.015
Scopus记录号: 2-s2.0-85043348208
论文题名:
Promotional effect of CH3I on hydroxycarbonylation of cycloalkene using homogeneous rhodium catalysts with PPh3 ligand
作者: Oku T.; Okada M.; Puripat M.; Hatanaka M.; Morokuma K.; Choi J.-C.
刊名: Journal of CO2 Utilization
ISSN: 22129820
出版年: 2018
卷: 25
起始页码: 1
结束页码: 5
语种: 英语
英文关键词: CO2 ; Formic acid ; Hydroxycarbonylation ; Organorhodium complex ; Reaction mechanism
Scopus关键词: Catalysts ; Chlorine compounds ; Coordination reactions ; Formic acid ; Free energy ; Hydrides ; Ligands ; Rhodium ; 14-electron complex ; Cyclohexanecarboxylic acids ; Free energy of formations ; Hydroxycarbonylation ; Organorhodium complex ; Promotional effect ; Reaction mechanism ; Rhodium catalysts ; Rhodium compounds
英文摘要: The reaction mechanism of the hydroxycarbonylation of cyclohexene with formic acid to form cyclohexanecarboxylic acid using organorhodium complexes was investigated both experimentally and computationally. It was found that excess CH3I and PPh3 promote this reaction. The active catalyst species was determined to be a five-coordinated rhodium hydride 16-electron complex derived from a mononuclear rhodium 16-electron complex (Vaska-type complex). PPh3 and CH3I played the following roles: i) to promote the formation of the Vaska-type Rh complex from Rh2Cl2(CO)4 (1), ii) to aid the elimination of the PPh3 ligand from the Vaska-type complex by stabilizing the free energy of formation of a mononuclear three-coordinated rhodium 14-electron complex through the formation of phosphonium iodide ([Ph3P(CH3)]I), and iii) to generate the active rhodium hydride species. © 2018 Published by Elsevier Ltd.
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资源类型: 期刊论文
标识符: http://119.78.100.158/handle/2HF3EXSE/111906
Appears in Collections:气候减缓与适应

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作者单位: Graduate School of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki, 305-8573, Japan; Research Center, Nippon Shokubai Co., Ltd., 5-8 Nishi, Otabi-cho, Suita, Osaka, 564-0034, Japan; Research Association of High-Throughput Design and Development for Advanced Function Material, Tsukuba Central 5, 1-1-1 Higashi, Tsukuba, Ibaraki, 305-8565, Japan; Fukui Institute for Fundamental Chemistry, Kyoto University, 34-4 Takano-Nishihiraki-cho, Sakyou-ku, Kyoto, 606-8103, Japan; Institute for Research Initiatives, Graduate School of Materials Science and Data Science Center, Nara Institute of Science and Technology, 8916-5 Takayama-cho, Ikoma, Nara, 630-0192, Japan; National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba Central 5, 1-1-1 Higashi, Tsukuba, Ibaraki, 305-8565, Japan

Recommended Citation:
Oku T.,Okada M.,Puripat M.,et al. Promotional effect of CH3I on hydroxycarbonylation of cycloalkene using homogeneous rhodium catalysts with PPh3 ligand[J]. Journal of CO2 Utilization,2018-01-01,25
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