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

doi:10.6023/cjoc202507040

Chinese Journal of Organic Chemistry ›› 2026, Vol. 46 ›› Issue (2): 507-514.DOI: 10.6023/cjoc202507040 Previous Articles Next Articles

ARTICLES

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

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 发布日期:2025-11-05
通讯作者: 王力为, 戚孝天
基金资助:
中央高校基本科研业务费专项资金(2042025kf0052)

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

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

^a College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072
^b The Institute for Advanced Studies, Wuhan University, Wuhan 430072

Received:2025-07-29 Revised:2025-10-03 Published:2025-11-05
Contact: Liwei Wang, Xiaotian Qi
Supported by:
Fundamental Research Funds for the Central Universities(2042025kf0052)

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

Cite this article

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.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 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.

References 42

[1]	a) Novotny J. A.; Peterson C. A. Adv. Nutr. 2018, 9, 272.
	( (b) Hu C.-Z. J.;Huang Z. D.; Fu H. H.; Peng X. H. Chin. J. Org. Chem. 2018, 38, 486 (in Chinese).
	( 胡传峰, 周建豪, 黄志达, 傅惠惠, 彭新华, 有机化学, 2018, 38, 486.)
	( (c) Li C.-S.; Chun C. L. Chin. J. Org. Chem. 2001, 21, 1009 (in Chinese).
	( 宋礼成, 罗春成, 有机化学, 2001, 21, 1009.)
[2]	Metz S.; Thiel W. Coord. Chem. Rev. 2011, 255, 1085.
[3]	a) Hille R. Chem. Rev. 1996, 96, 2757.
	(b) Hille R. Trends Biochem. Sci 2002, 27, 360.
	(c) Mendel R. R. Dalton Trans. 2005, 3404.
[4]	a) Lennartson A. Nat. Chem. 2014, 6, 746.
	(b) Carmona E. Chem. Eur. J. 2019, 25, 11.
[5]	a) Schrock R. R. Angew. Chem. Int. Ed. 2006, 45, 3748.
	(b) Nguyen T. T.; Koh M. J.; Shen X.; Romiti F.; Schrock R. R.; Hoveyda A. H. Science 2016, 352, 569.
	(c) Korber J. N.; Wille C.; Leutzsch M.; Fürstner A. J. Am. Chem. Soc. 2023, 145, 26993.
[6]	Margulieux G. W.; Bezdek M. J.; Turner Z. R.; Chirik P. J. J. Am. Chem. Soc. 2017, 139, 6110.
[7]	Poli R. Chem. Eur. J. 2004, 10, 332.
[8]	a) Hille R.; Hall J.; Basu P. Chem. Rev. 2014, 114, 3963.
	(b) McSkimming A.; Suess D. L. M. Nat. Chem. 2021, 13, 666.
	(c) Miyazaki T.; Tanaka H.; Tanabe Y.; Yuki M.; Nakajima K.; Yoshizawa K.; Nishibayashi Y. Angew. Chem. Int. Ed. 2014, 53, 11488.
	(d) Lehnert N.; Musselman B. W.; Seefeldt L. C. Chem. Soc. Rev. 2021, 50, 3640.
[9]	a) Hu Z.-N.; Ai Y.; Zhao Y.; Wang Y.; Ding K.; Zhang W.; Guo R.; Zhang X.; Cai X.; Wang N.; Hu J.; Liang Q.; Liu H.; Huang F.; Wu L.; Zhang J.; Sun H.-B. Nano Res. 2023, 16, 2302.
	(b) Wang L.; Liu X.; Zhang Q.; Zhou G.; Pei Y.; Chen S.; Wang J.; Rao A. M.; Yang H.; Lu B. Nano Energy 2019, 61, 194.
[10]	Cao L.-Y.; Luo J.-N.; Yao J.-S.; Wang D.-K.; Dong Y.-Q.; Zheng C.; Zhuo C.-X. Angew. Chem. Int. Ed. 2021, 60, 15254.
[11]	Dong Y.-Q.; Shi X.-N.; Cao L.-Y.; Bai J.; Zhuo C.-X. Org. Chem. Front. 2023, 10, 3544.
[12]	Qing H.-S, Bao X. G. Chin. J. Org. Chem. 2024, 44, 3518 (in Chinese).
	( 孙庆浩, 鲍晓光, 有机化学, 2024, 44, 3518.)
[13]	a) Rui Y.; Chen Y.; Ivanova E.; Kumar V. B.; Śmiga S.; Grabowski I.; Dral P. O. Adv. Sci. 2024, 11, 2408239.
	(b) Licht R. B.; Bell A. T. ACS Catal. 2017, 7, 161.
[14]	a) Ziane M.; Amitouche F.; Bouarab S.; Vega A. J. Nanopart. Res. 2017, 19, 380.
	(b) Mallick S.; Lu Y.; Luo M. H.; Meng M.; Tan Y. N.; Liu C. Y.; Zuo J.-L. Inorg. Chem. 2017, 56, 14888.
[15]	a) Kanungo B.; Zimmerman P. M.; Gavini V. Nat. Commun. 2019, 10, 4497.
	(b) Su N. Q.; Xu X. Annu. Rev. Phys. Chem. 2017, 68, 155.
[16]	Oueis Y.; Staroverov V. N. J. Chem. Phys 2022, 157, 204107.
[17]	Albavera-Mata A.; Botello-Mancilla K.; Trickey S. B.; Gázquez J. L.; Vela A. Phys. Rev. B 2020, 102, 035129.
[18]	Gould T.; Pittalis S. Phys. Rev. X 2024, 14, 041045.
[19]	Garza A. J.; Bell A. T.; Head-Gordon M. J. Chem. Theory Comput. 2018, 14, 3083.
[20]	Frisch, M. J. T. G. W.; Schlegel H. B.; Scuseria G. E.; Robb M. A.; Cheeseman J. R.; Scalmani G.; Barone V.; Mennucci B.; Petersson G. A.; Nakatsuji H.; Caricato M.; Li X.; Hratchian H. P.; Izmaylov A. F.; Bloino J.; Zheng G.; Sonnenberg J. L.; Hada M.; Ehara M.; Toyota K.; Fukuda R.; Hasegawa J.; Ishida M.; Nakajima T.; Honda Y.; Kitao O.; Nakai H.; Vreven T.; Montgomery J. A., Jr.; ; Peralta J. E.; Ogliaro F.; Bearpark M.; Heyd J. J.; Brothers E.; Kudin K. N.; Staroverov V. N.; Kobayashi R.; Normand J.; Raghavachari K.; Rendell A.; Burant J. C.; Iyengar S. S.; Tomasi J.; Cossi M.; Rega N.; Millam N. J.; Klene M.; Knox J. E.; Cross J. B.; Bakken V.; Adamo C.; Jaramillo J.; Gomperts R.; Stratmann R. E.; Yazyev O.; Austin A. J.; Cammi R.; Pomelli C.; Ochterski J. W.; Martin R. L.; Morokuma K.; Zakrzewski V. G.; Voth G. A.; Salvador P.; Dannenberg J. J.; Dapprich S.; Daniels A. D.; Farkas O.; Foresman J. B.; Ortiz J. V.; Cioslowski J.; Fox D. J. Gaussian 16, Revision C.01; Gaussian, Inc.: Wallingford, CT, 2019.
[21]	a) Neese F. WIREs Comput. Mol. Sci. 2012, 2, 73.
	(b) Neese F. WIREs Comput. Mol. Sci. 2018, 8, e1327.
	(c) Neese F.; Wennmohs F.; Becker U.; Riplinger C. J. Chem. Phys. 2020, 152, 224108.
[22]	Verma P.; Truhlar D. G. Trends Chem. 2020, 2, 302.
[23]	Perdew J. P. Phys. Rev. B 1986, 33, 8822.
[24]	a) Stephens P. J.; Devlin F. J.; Chabalowski C. F.; Frisch M. J. J. Phys. Chem. 1994, 98, 11623.
	(b) Becke A. D. J. Chem. Phys 1993, 98, 5648.
[25]	Adamo C.; Barone V. J. Chem. Phys. 1999, 110, 6158.
[26]	Shimazaki T.; Nakajima T. Chem. Phys. Lett. 2016, 647, 132.
[27]	Grimme S.; Antony J.; Ehrlich S.; Krieg H. J. Chem. Phys. 2010, 132, 154104.
[28]	Chai J.-D.; Head-Gordon M. Phys. Chem. Chem. Phys. 2008, 10, 6615.
[29]	Zhao Y.; Truhlar D. G. J. Chem. Phys. 2006, 125, 194101.
[30]	Peverati R.; Truhlar D. G. J. Phys. Chem. Lett. 2012, 3, 117.
[31]	Yu H. S.; He X.; Truhlar D. G. J. Chem. Theory Comput. 2016, 12, 1280.
[32]	Zhao Y.; Truhlar D. G. Theor. Chem. Acc. 2008, 120, 215.
[33]	Peverati R.; Truhlar D. G. J. Phys. Chem. Lett. 2011, 2, 2810.
[34]	Yu H. S.; He X.; Li S. L.; Truhlar D. G. Chem. Sci. 2016, 7, 5032.
[35]	a) Tao J.; Perdew J. P.; Staroverov V. N.; Scuseria G. E. Phys. Rev. Lett. 2003, 91, 146401.
	(b) Staroverov V. N.; Scuseria G. E.; Tao J.; Perdew J. P. J. Chem. Phys. 2004, 121, 11507.
[36]	Xu X.; Goddard W. A. Proc. Natl. Acad. Sci. 2004, 101, 2673.
[37]	Gray M.; Herbert J. M. J. Chem. Phys 2024, 161, 054114.
[38]	a) Weigend F.; Ahlrichs R. Phys. Chem. Chem. Phys. 2005, 7, 3297.
	(b) Weigend F. Phys. Chem. Chem. Phys. 2006, 8, 1057.
[39]	Marenich A. V.; Cramer C. J.; Truhlar D. G. J. Phys. Chem. B. 2009, 113, 6378.
[40]	a) Weigend F. J. Comput. Chem. 2008, 29, 167.
	(b) Hellweg A.; Hättig C.; Höfener S.; Klopper W. Theor. Chem. Acc. 2007, 117, 587.
[41]	Legault C. Y. C. 1.0b, Université de Sherbrooke, Sher-brooke, Quebec, Canada, 2009, http://www Cylview.org.
[42]	Li W.; Huang M.; Liu J.; Huang Y.-L.; Lan X.-B.; Ye Z.; Zhao C.; Liu Y.; Ke Z. ACS Catal. 2021, 11, 10377.

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

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

RichHTML

PDF

Knowledge

Abstract

Cite this article

share this article

Fig. & Tab. 6

References 42

Related Articles 5

Recommended Articles

Metrics

Comments

[1]	Yuanhe Zhang, Yunjie Shen, Dongxing Tan, Fushe Han. Study on the Cyclopropanation Reactivity and Selectivity of Spiroannulated Pentacyclic Diastereoisomers toward Synthesizing Cryptoquinonemethides [J]. Chinese Journal of Organic Chemistry, 2026, 46(1): 96-105.
[2]	Xiaopeng Ling, Shaoping Tao, Qi Lin, Bingbing Shi, Hong Yao, Taibao Wei, Jinfa Chen. A Pillar[5]arene-Based π-Conjugated Dye Used for Fluorescence Sensing of L-Arginine [J]. Chinese Journal of Organic Chemistry, 2025, 45(7): 2480-2485.
[3]	Qinghao Sun, Xiaoguang Bao. Computational Insights into the Mechanism of the Mo-Catalyzed Deoxygenative Coupling of Aromatic Aldehydes [J]. Chinese Journal of Organic Chemistry, 2024, 44(11): 3518-3525.
[4]	Xuewei Chen, Fangcai Yu, Chuanhong Tian. 1,1'-Methylenediimidazolium-Based Multiple Hydrogen-Bond Donor Catalysts Facilitate the Cycloaddition of CO₂ with Epoxides under Atmospheric Pressure [J]. Chinese Journal of Organic Chemistry, 2024, 44(10): 3198-3205.
[5]	Man Xu, Yuanzhi Xia. Mechanistic Understanding of Rh(III)-Catalyzed Redox-Neutral C—H Activation/Annulation Reactions of N-Phenoxyacetamides and Methyleneoxetanones [J]. Chinese Journal of Organic Chemistry, 2021, 41(8): 3272-3278.