Promotional effect of CH3I on hydroxycarbonylation of cycloalkene using homogeneous rhodium catalysts with PPh3 ligand

Tomoharu Oku; Masaki Okada; Maneeporn Puripat; Miho Hatanaka; Keiji Morokuma; Jun Chul Choi

doi:10.1016/j.jcou.2018.02.015

Promotional effect of CH₃I on hydroxycarbonylation of cycloalkene using homogeneous rhodium catalysts with PPh₃ ligand

Tomoharu Oku, Masaki Okada, Maneeporn Puripat, Miho Hatanaka, Keiji Morokuma, Jun Chul Choi

Research output: Contribution to journal › Article › peer-review

1 Citation (Scopus)

Abstract

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.

Original language	English
Pages (from-to)	1-5
Number of pages	5
Journal	Journal of CO2 Utilization
Volume	25
DOIs	https://doi.org/10.1016/j.jcou.2018.02.015
Publication status	Published - 2018 May
Externally published	Yes

Keywords

CO
Formic acid
Hydroxycarbonylation
Organorhodium complex
Reaction mechanism

ASJC Scopus subject areas

Chemical Engineering (miscellaneous)
Waste Management and Disposal
Process Chemistry and Technology

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title = "Promotional effect of CH3I on hydroxycarbonylation of cycloalkene using homogeneous rhodium catalysts with PPh3 ligand",

abstract = "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.",

keywords = "CO, Formic acid, Hydroxycarbonylation, Organorhodium complex, Reaction mechanism",

author = "Tomoharu Oku and Masaki Okada and Maneeporn Puripat and Miho Hatanaka and Keiji Morokuma and Choi, {Jun Chul}",

note = "Funding Information: This work is based on the results obtained under a project (P16010) commissioned by the New Energy and Industrial Technology Development Organization (NEDO), Japan. We thank Prof. Dr. Shigeyoshi Sakaki, Fukui Institute for Fundamental Chemistry, Kyoto University, Japan; Dr. Yoongkee Choe, CD-FMat, National Institute of Advanced Industrial Science and Technology, Japan; and Mr. Satoshi Ishida, Nippon Shokubai Co., Ltd., Japan, for valuable discussions. Publisher Copyright: {\textcopyright} 2018 Published by Elsevier Ltd.",

year = "2018",

month = may,

doi = "10.1016/j.jcou.2018.02.015",

language = "English",

volume = "25",

pages = "1--5",

journal = "Journal of CO2 Utilization",

issn = "2212-9820",

publisher = "Elsevier BV",

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T1 - Promotional effect of CH3I on hydroxycarbonylation of cycloalkene using homogeneous rhodium catalysts with PPh3 ligand

AU - Oku, Tomoharu

AU - Okada, Masaki

AU - Puripat, Maneeporn

AU - Hatanaka, Miho

AU - Morokuma, Keiji

AU - Choi, Jun Chul

N1 - Funding Information: This work is based on the results obtained under a project (P16010) commissioned by the New Energy and Industrial Technology Development Organization (NEDO), Japan. We thank Prof. Dr. Shigeyoshi Sakaki, Fukui Institute for Fundamental Chemistry, Kyoto University, Japan; Dr. Yoongkee Choe, CD-FMat, National Institute of Advanced Industrial Science and Technology, Japan; and Mr. Satoshi Ishida, Nippon Shokubai Co., Ltd., Japan, for valuable discussions. Publisher Copyright: © 2018 Published by Elsevier Ltd.

PY - 2018/5

Y1 - 2018/5

N2 - 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.

AB - 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.

KW - CO

KW - Formic acid

KW - Hydroxycarbonylation

KW - Organorhodium complex

KW - Reaction mechanism

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