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DFT study on the synthesis of trifluoroacetophenone from palladium complex LnPd(Ph)CF3 (Ln = Xantphos or DtBPF) and CO

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Abstract

The carbonylative trifluoromethylation reaction mechanism of palladium complex LnPd(Ph)CF3 (Ln = Xantphos or DtBPF) and CO to synthesize trifluoroacetophenone was calculated using the density functional theory B3LYP method. In this paper, we conducted a computational study on the competition mechanism of two different products trifluorotoluene and trifluoroacetophenone. The calculation result reveals (1) CO insertion and reduction-elimination are two key steps in palladium-catalyzed reactions; (2) for the palladium complex (Xantphos)Pd(Ph)CF3, the resulting product trifluoroacetyl has a lower activation energy and higher reactivity; and (3) for the metal palladium ligand DtBPF, the small energy difference between the two products indicates that the stereoselectivity of the product is relatively poor. The computational research results in this paper provide a good supplement and effective explanation to the experimental phenomenon of Domino et al. (Organometallics 39:688–697, 2020).

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Acknowledgements

We are grateful to the reviewers for their invaluable suggestions.

Funding

This work was supported by Natural Science Foundation of Gansu Province (20JR5RA479 of Prof. Xinghui Zhang) and the Outstanding Youth Research Program of Lanzhou University of Arts and Sciences (2021SZZX06 of Prof. Xinghui Zhang).

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Authors and Affiliations

  1. School of Chemical Engineering, Lanzhou University of Arts and Science, Lanzhou, 730010, China

    XingXui Zhang, HaiXiong Shi, ZiYi Wang & ShanShan Li

  2. School of Foreign Languages, Lanzhou University of Arts and Science, Lanzhou, 730010, China

    Xi Wu

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Contributions

XingHui Zhang: problem selection, writing, and data analysis.

Xi Wu: result analysis, manuscript editing.

HaiXiong Shi: simulations, analysis, manuscript first draft.

ZiYi Wang: methods, project management, result analysis, manuscript editing.

ShanShan Li: data analysis, writing.

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Correspondence to XingXui Zhang.

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Zhang, X., Wu, X., Shi, H. et al. DFT study on the synthesis of trifluoroacetophenone from palladium complex LnPd(Ph)CF3 (Ln = Xantphos or DtBPF) and CO. J Mol Model 28, 48 (2022). https://doi.org/10.1007/s00894-022-05030-0

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