Promotional effect of CH3I on hydroxycarbonylation of cycloalkene using homogeneous rhodium catalysts with PPh3 ligand
| Autor: | Tomoharu Oku, Maneeporn Puripat, Jun-Chul Choi, Keiji Morokuma, Masaki Okada, Miho Hatanaka |
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| Rok vydání: | 2018 |
| Předmět: |
Reaction mechanism
010405 organic chemistry Ligand Chemistry Hydride Process Chemistry and Technology Cyclohexene chemistry.chemical_element 010402 general chemistry 01 natural sciences 0104 chemical sciences Catalysis Rhodium chemistry.chemical_compound Polymer chemistry Chemical Engineering (miscellaneous) Phosphonium Waste Management and Disposal Cycloalkene |
| Zdroj: | Journal of CO2 Utilization. 25:1-5 |
| ISSN: | 2212-9820 |
| DOI: | 10.1016/j.jcou.2018.02.015 |
| Popis: | 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. |
| Databáze: | OpenAIRE |
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