Theoretical Study on Mechanism of Hydroformylation of Ethene Catalyzed by a Heterobimetallic Rh(I)‐Cr Complex

Abstract

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.

Heterogeneous ethylene hydroformylation on polymer supported Rh-based catalysts: a DFT analysis of the mechanism and Rh–P effect

“…In addition, by comparing the research of Tang et al 28 on the homogeneous catalysis of ethylene hydroformylation by Rh–Cr based catalysts, in which the energy barriers of the key steps of the reaction are 14.70 kJ mol −1 and 21.86 kcal mol −1 (units are converted) in the two mechanisms, respectively, it was found that the energy barriers of the key steps of the reaction of the two crosslinking modes studied in this paper are lower, indicating that the reaction is more likely to occur.…”