Determination of Key Intermediates for Homogeneous Water-gas Shift Reaction and Hydrocarbonylation of Ethylene to Diethyl Ketone Catalyzed by the ’Pd(OAc)2-PPh3-CF3COOH/H2O’ System Научная публикация
| Журнал |
Journal of Molecular Catalysis (Continued after 1994 as Journal of Molecular Catalysis A: Chemical and Journal of Molecular Catalysis B: Enzymatic)
ISSN: 0304-5102 |
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| Вых. Данные | Год: 1989, Том: 52, Номер: 1, Страницы: 27-48 Страниц : 22 DOI: 10.1016/0304-5102(89)80080-X | ||
| Ключевые слова | ethylene hydrocarbonylation palladium catalyst; water gas shift intermediate | ||
| Авторы |
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| Организации |
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Реферат:
The homogeneous water-gas shift reaction (WGSR) and hydrocarbonylation of ethylene to diethyl ketone (DEK) catalyzed by the ‘Pd(OAc)2-PPh3-CF3COOH/H2O’ system have been studied. The main kinetic regularities of these reactions have been elucidated, and the catalytically active palladium species have been detected and characterized by 1H, 13C and 31P NMR. The key palladium intermediate for both catalytic reactions is the cationic hydride complex [(PPh3)3PdH]+ 1. In the case of the WGSR, this complex serves as a source of dihydrogen, and in the case of the hydrocarbonylation of ethylene it undergoes transformations via consecutive rapid insertions of C2H4 into a Pd-H bond and then of CO into a Pd-C bond to form, respectively, palladium ethyl and propionyl complexes. All the kinetic and NMR data obtained support the mechanism involving the phosphinepalladium(II) complex reduction with CO to form CO2 as the rate-determining step for the WGSR, and the mechanism involving formation of the species 1 and the palladium propionyl complex interaction with C2H4 as slow steps for the hydrocarbonylation of ethylene with CO/H2 to give DEK. The possible reasons for the relative stability of the palladium hydride, ethyl and propionyl complexes in strongly acidic medium and the high selectivity of DEK formation in the hydrocarbonylation reaction are discussed.
Библиографическая ссылка:
Zudin V.N.
, Chinakov V.D.
, Nekipelov V.M.
, Rogov V.A.
, Likholobov V.A.
, Yermakov Y.I.
Determination of Key Intermediates for Homogeneous Water-gas Shift Reaction and Hydrocarbonylation of Ethylene to Diethyl Ketone Catalyzed by the ’Pd(OAc)2-PPh3-CF3COOH/H2O’ System
Journal of Molecular Catalysis (Continued after 1994 as Journal of Molecular Catalysis A: Chemical and Journal of Molecular Catalysis B: Enzymatic). 1989. V.52. N1. P.27-48. DOI: 10.1016/0304-5102(89)80080-X WOS Scopus РИНЦ CAPlusCA OpenAlex
Determination of Key Intermediates for Homogeneous Water-gas Shift Reaction and Hydrocarbonylation of Ethylene to Diethyl Ketone Catalyzed by the ’Pd(OAc)2-PPh3-CF3COOH/H2O’ System
Journal of Molecular Catalysis (Continued after 1994 as Journal of Molecular Catalysis A: Chemical and Journal of Molecular Catalysis B: Enzymatic). 1989. V.52. N1. P.27-48. DOI: 10.1016/0304-5102(89)80080-X WOS Scopus РИНЦ CAPlusCA OpenAlex
Даты:
| Опубликована в печати: | 22 июн. 1989 г. |
| Опубликована online: | 2 окт. 2001 г. |
Идентификаторы БД:
| Web of science: | WOS:A1989U855600004 |
| Scopus: | 2-s2.0-0003007736 |
| РИНЦ: | 30840293 |
| Chemical Abstracts: | 1989:441774 |
| Chemical Abstracts (print): | 111:41774 |
| OpenAlex: | W2043116191 |