Title: Density functional computations of Rh(I)-catalysed hydroacylation of acetic aldehyde and ethene
Abstract: Abstract Density functional theory has been used to study Rh(I)-catalysed hydroacylation of acetic aldehyde and ethene. All the intermediates and the transition states were optimised completely at the B3LYP/6-311+ + G(d,p) level (LANL2DZ(d) for Rh, P). Calculation results confirm that Rh(I)-catalysed hydroacylation of acetic aldehyde and ethene is endothermic, and the total absorbed energy is about 47 kJ/mol. The hydroacylation involves four possible reaction channels, going mainly through Rh–ethene–aldehyde complexes, Rh–ethene–carbonyl complexes, Rh-ethanyl-carbonyl complexes, and Rh-ketone complexes. The formation of Rh–ethene–carbonyl complexes (i.e. Rh(I)-catalysed oxidative addition of aldehyde) is the rate-determinating step for the Rh(I)-catalysed hydroacylation. And the energy barriers of the H-transfer reaction are lower than those of the C–C bond-forming reaction, and thus the H-transfer reaction is prior to the C–C bond-forming reaction. Therefore, the dominant reaction channels predicted theoretically are the reaction channels “a” and “b”, which is well in agreement with the experiments. Keywords: Rh-catalysed hydroacylationacetic aldehydeethenereaction mechanismDFT
Publication Year: 2008
Publication Date: 2008-04-01
Language: en
Type: article
Indexed In: ['crossref']
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Cited By Count: 6
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