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Theoretical Study on Mechanism of Hydroformylation of Ethene Catalyzed by a Heterobimetallic Rh(I)‐Cr Complex
Author(s) -
TANG Dianyong,
ZHANG Yuanqin,
HU Changwei
Publication year - 2009
Publication title -
chinese journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.28
H-Index - 41
eISSN - 1614-7065
pISSN - 1001-604X
DOI - 10.1002/cjoc.200990030
Subject(s) - chemistry , hydroformylation , moiety , aldehyde , catalysis , associative substitution , catalytic cycle , density functional theory , mechanism (biology) , reaction mechanism , computational chemistry , photochemistry , medicinal chemistry , stereochemistry , rhodium , organic chemistry , philosophy , epistemology
The mechanism of ethene hydroformylation catalyzed by a heterobimetallic complex HRh(CO)(PH 3 )(µ‐PH 2 ) 2 ‐ Cr(CO) 4 was investigated by density functional theory (DFT). Both the associative and dissociative mechanisms were studied, and the results were compared. It was found that the introduction of Cr(CO) 4 moiety did not remodel the mechanism of hydroformylation of simple alkenes. The dissociative mechanism is predominant. The carbonyl insertion is the rate‐limiting step for the whole catalytic cycle with a free energy barrier of 91.15 kJ/mol at 298.15 K and 101.325 kPa. The aldehyde elimination step was predicted to be irreversible. These results are in good agreement with the previous theoretical and experimental studies.