铁卟啉催化氧化邻、对硝基取代芳烃α-C-H键的密度泛函理论研究

doi:10.11896/cldb.21110223

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Abstract The catalytic oxidations of α-C-H bond in o-nitro-substituted arenes and p-nitro-substituted arenes (toluene, ethylbenzene and cumene) by iron porphyrin were studied using density functional theory. The calculation results were compared with those of α-C-H bond oxidation in arenes without nitro substituent. The reactivity difference of α-C-H bond oxidation between o-nitro-substituted arenes and p-nitro-substituted arenes catalyzed by iron porphyrin were focused on and the essential factors affecting the reactivity were explored. By calculating the bond dissociation energy of α-C-H bond and the activation energy of α-C-H bond oxidation in arenes by iron porphyrin, it is found that the conjugation effect between nitro and benzene ring in p-nitro-substituted arenes reduce the bond dissociation energy of α-C-H bond and the activation energy of α-C-H bond oxidation by high-valent iron-oxo porphyrin. In o-nitro-substituted arenes, there are not only conjugation effect, but also steric hindrance effect. The steric hindrance effect is dominant in o-nitro-substituted arenes. The bond dissociation energy of α-C-H bond and the activation energy of α-C-H bond oxidation by high-valent iron-oxo porphyrin increase due to the steric hindrance effect. Further decomposition of the activation energy of α-C-H bond oxidation reveals that the interaction energy between the arene and high-valent iron-oxo porphyrin in the transition structure is relatively weak and the distortion energy is the main factor affecting the activation energy. The distortion energy mainly comes from the distortion of the arene molecule.

Key words： iron porphyrin catalytic oxidation arene α-C-H bond density functional theory

Published: 25 April 2023 Online: 2023-04-24

CLC number:

O643.3

Fund:National Natural Science Foundation of China (21776021) and Beijing Outstanding Young Scientists Projects (BJJWZYJH0201910005017).

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	GUO Jing
	SONG Xufeng
	YU Yanmin
	GAO Qianqian

Cite this article:

GUO Jing,SONG Xufeng,YU Yanmin, et al. Density Functional Theory Study on α-C-H Bond Oxidation of o-Nitro-Substituted Arenes and p-Nitro-Substituted Arenes Catalyzed by Iron Porphyrin[J]. Materials Reports, 2023, 37(8): 21110223-6.

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http://www.mater-rep.com/EN/10.11896/cldb.21110223 OR http://www.mater-rep.com/EN/Y2023/V37/I8/21110223

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