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Mechanism of intermolecular hydroacylation of vinylsilanes catalyzed by a rhodium(I) olefin complex: a DFT study

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Abstract

Density functional theory (DFT) was used to investigate the Rh(I)-catalyzed intermolecular hydroacylation of vinylsilane with benzaldehyde. All intermediates and transition states were optimized completely at the B3LYP/6-31G(d,p) level (LANL2DZ(f) for Rh). Calculations indicated that Rh(I)-catalyzed intermolecular hydroacylation is exergonic, and the total free energy released is −110 kJ mol−1. Rh(I)-catalyzed intermolecular hydroacylation mainly involves the active catalyst CA2, rhodium–alkene–benzaldehyde complex M1, rhodium–alkene–hydrogen–acyl complex M2, rhodium–alkyl–acyl complex M3, rhodium–alkyl–carbonyl–phenyl complex M4, rhodium–acyl–phenyl complex M5, and rhodium–ketone complex M6. The reaction pathway CA2 + R2 → M1b → T1b → M2b → T2b1 → M3b1 → T4b → M4b → T5b → M5b → T6b → M6b → P2 is the most favorable among all reaction channels of Rh(I)-catalyzed intermolecular hydroacylation. The reductive elimination reaction is the rate-determining step for this pathway, and the dominant product predicted theoretically is the linear ketone, which is consistent with Brookhart’s experiments. Solvation has a significant effect, and it greatly decreases the free energies of all species. The use of the ligand Cp′ (Cp′ = C5Me4CF3) decreased the free energies in general, and in this case the rate-determining step was again the reductive elimination reaction.

Rh(I)-catalyzed intermolecular hydroacylation was investigated using density functional theory (DFT). This study suggests that the hydroacylation is exergonic, and that the dominant product is the linear ketone

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Acknowledgments

This work was supported by the Key Project of Science and Technology of the Ministry of Education, P.R. (grant no. 104263), Natural Science Foundation of Chongqing City, P.R. (grant no. CSTC-2004BA4024).

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  1. College of Chemistry and Chemical Engineering, Southwest University, Chongqing, 400715, People’s Republic of China

    Qingxi Meng, Wei Shen & Ming Li

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  1. Qingxi Meng
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  2. Wei Shen
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Correspondence to Ming Li.

Electronic supplementary material

Computational details about the energies and detailed structures of the stationary points in the reactions are given in the electronic supplementary material.

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Meng, Q., Shen, W. & Li, M. Mechanism of intermolecular hydroacylation of vinylsilanes catalyzed by a rhodium(I) olefin complex: a DFT study. J Mol Model 18, 1229–1239 (2012). https://doi.org/10.1007/s00894-011-1151-z

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