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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 Full article

Journal Journal of Molecular Catalysis (Continued after 1994 as Journal of Molecular Catalysis A: Chemical and Journal of Molecular Catalysis B: Enzymatic)
ISSN: 0304-5102
Output data Year: 1989, Volume: 52, Number: 1, Pages: 27-48 Pages count : 22 DOI: 10.1016/0304-5102(89)80080-X
Tags ethylene hydrocarbonylation palladium catalyst; water gas shift intermediate
Authors Zudin V.N. 1 , Chinakov V.D. 1 , Nekipelov V.M. 1 , Rogov V.A. 1 , Likholobov V.A. 1 , Yermakov Yu.I. 1
Affiliations
1 Institute of Catalysis

Abstract: 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.
Cite: 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 ANCAN OpenAlex
Dates:
Published print: Jun 22, 1989
Published online: Oct 2, 2001
Identifiers:
Web of science: WOS:A1989U855600004
Scopus: 2-s2.0-0003007736
Elibrary: 30840293
Chemical Abstracts: 1989:441774
Chemical Abstracts (print): 111:41774
OpenAlex: W2043116191
Citing:
DB Citing
Web of science 97
Scopus 94
Elibrary 95
OpenAlex 90
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