钼催化羰基氧化加成步骤的密度泛函理论(DFT)方法评估研究

doi:10.6023/cjoc202507040

摘要/Abstract

在钼化学中, 邻苯醌或1,2-二羰基化合物对钼的氧化加成被广泛应用于钼催化的碳碳成键反应. 其中羰基对零价或者二价钼的协同氧化加成是钼催化的关键基元步骤. 关于该基元步骤的密度泛函理论(DFT)计算研究相对较少, 特别是对泛函的选取缺少参考. 因此, 选择了14种密度泛函计算钼催化的羰基氧化加成过程, 评估了不同泛函对于结构优化和能量计算的准确性. 平均绝对误差(MAE)和平均平方误差(MSE)分析表明, B3LYP-D3(BJ)、TPSSh和ωB97X-D泛函在结构优化方面具有较好的表现. 此外, 基于B3LYP-D3(BJ)泛函在气相中优化得到的结构, 使用M06、M06-L和MN15-L泛函进行能量计算的结果与DLPNO-CCSD(T)泛函计算得到的数据更为接近, 特别是MN15-L的表现最优, 具有最小的MAE和MSE.

关键词: 钼催化, 羰基氧化加成, 密度泛函理论(DFT)计算, DFT方法评估

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 the smallest MAE and MSE.

Key words: molybdenum catalysis, carbonyl oxidation addition, density functional theory (DFT) calculation, DFT benchmark study

引用此文

陈梓桐, 王力为, 沈晓, 戚孝天. 钼催化羰基氧化加成步骤的密度泛函理论(DFT)方法评估研究[J]. 有机化学, 2026, 46(2): 507-514.

Zitong Chen, Liwei Wang, Xiao Shen, Xiaotian Qi. A Benchmark Study of Density Functional Theory (DFT) Methods for Mo-Catalyzed Carbonyl Oxidative Addition[J]. Chinese Journal of Organic Chemistry, 2026, 46(2): 507-514.

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图/表 6

Scheme 1. Mo-catalyzed carbonyl oxidative addition reactions

Figure 1. (a) X-ray crystal structure of Mo(0) catalysts 1 and 2; (b) MAE and MSE values of the benchmark results compared to the X-ray crystal structures

Figure 2. DFT study of three representative carbonyl oxidative addition steps in Mo catalysis The activation free energies were calculated using DLPNO-CCSD(T) based on the structures optimized by B3LYP-D3, ωB97X-D, and TPSSh, respectively. The 3D structures were optimized using B3LYP-D3(BJ).

Figure 3. Benchmark results of DFT functionals for energy calculation of TPSSh optimized carbonyl oxidative addition transition states The activation free energy calculated by DLPNO-CCSD(T) is used as the standard of energy.

Figure 4. Benchmark results of DFT functionals for energy calculation of ωB97X-D optimized carbonyl oxidative addition transition states The activation free energy calculated by DLPNO-CCSD(T) is used as the standard of energy.

Figure 5. Benchmark results of DFT functionals for energy calculation of B3LYP-D3(BJ) optimized carbonyl oxidative addition transition states The activation free energy calculated by DLPNO-CCSD(T) is used as the standard of energy.

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