A Benchmark Study of Density Functional Theory (DFT) Methods for Mo-Catalyzed Carbonyl Oxidative Addition

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.