A Benchmark Study of DFT Methods for Mo-catalyzed Carbonyl Oxidative Addition

doi:10.6023/cjoc202507040

Chinese Journal of Organic Chemistry

ARTICLE

钼催化羰基氧化加成步骤的DFT方法评估研究

陈梓桐^a, 王力为^a, 沈晓^b, 戚孝天^*,a

^a武汉大学化学与分子科学学院武汉 430072
^b武汉大学高等研究院武汉 430072

收稿日期:2025-07-29 修回日期:2025-10-03
基金资助:
中央高校基本科研业务费专项资金(No.2042025kf0052)资助项目.

A Benchmark Study of DFT Methods for Mo-catalyzed Carbonyl Oxidative Addition

Chen Zitong^a, Wang Liwei^a, Shen Xiao^b, Qi Xiaotian^*,a

^aCollege of Chemistry and Molecular Sciences, Wuhan University, Wuhan, 430072, China
^b1The Institute for Advanced Studies, Wuhan University, Wuhan, 430072, China

Received:2025-07-29 Revised:2025-10-03
Contact: *E-mail: qi7xiaotian@whu.edu.cn
Supported by:
Fundamental Research Funds for the Central Universities (2042025kf0052) and the supercomputing system in the Supercomputing Center of Wuhan University.

In molybdenum chemistry, the oxidative addition of o-quinone or 1,2-dicarbonyl compounds to molybdenum has been widely used in Mo-catalyzed C-C bond construction. The carbonyl oxidative addition to Mo(0) or Mo(II) is the critical elementary reaction of molybdenum catalysis. However, the relevant density functional theory (DFT) studies are relatively scarce, especially regarding the rational selection of functionals. In this work, 14 functionals were employed to investigate the Mo-catalyzed carbonyl oxidative addition step. A benchmark study was carried out to evaluate their performance in structure optimization and energy calculation. Analyses of mean absolute error (MAE) and mean squared error (MSE) indicated that the B3LYP-D3(BJ), TPSSh, and ωB97X-D functionals exhibited superior performance in structure optimization. Using the DLPNO-CCSD(T) functional as the reference, the M06, M06-L, and MN15-L functionals exhibited good performance for energy calculation based on the structures optimized using the B3LYP-D3(BJ) functional. In particular, MN15-L provided the best performance with MAE and MSE.

Key words: Molybdenum catalysis, Carbonyl oxidation addition, DFT calculation, Benchmark study

Cite this article

Chen Zitong, Wang Liwei, Shen Xiao, Qi Xiaotian. A Benchmark Study of DFT Methods for Mo-catalyzed Carbonyl Oxidative Addition[J]. Chinese Journal of Organic Chemistry, doi: 10.6023/cjoc202507040.

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钼催化羰基氧化加成步骤的DFT方法评估研究

A Benchmark Study of DFT Methods for Mo-catalyzed Carbonyl Oxidative Addition

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