Citation: Qi ZENG, Yan XU, Hua-Bin CHEN, Xuan XU, Zhi-Guang XU, Hai-Yang LIU. Oxygen Atom Transfer Reaction Mechanism between Manganese(Ⅴ)-Oxo Corrole Complexes and Styrene[J]. Chinese Journal of Inorganic Chemistry, ;2022, 38(1): 39-45. doi: 10.11862/CJIC.2022.005 shu

Oxygen Atom Transfer Reaction Mechanism between Manganese(Ⅴ)-Oxo Corrole Complexes and Styrene

Qi ZENG ¹ ,
Yan XU ¹ ,
Hua-Bin CHEN ¹ ,
Xuan XU ¹ ,
Zhi-Guang XU ^1,, ,
Hai-Yang LIU ^2,,

1.
School of Chemistry, South China Normal University, Guangzhou 510006, China
2.
School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510641, China

Corresponding author: Zhi-Guang XU, chzgxu@scnu.edu.cn Hai-Yang LIU, chhyliu@scut.edu.cn
Received Date: 16 May 2021
Revised Date: 20 October 2021

Figures(5)

The oxygen atom transfer (OAT) reaction pathway of the reaction between styrene and manganese(Ⅴ)-oxo corrole complexes (Mn^ⅤO corrole) was investigated using the density functional theory B3LYP method. The calculation results showed that the oxygen atom attacked the β carbon atom of the olefinic double bond in styrene to form a transition state, and the direct oxygen atom transfer pathway was determined via the intrinsic reaction coordinate method (IRC) and the minimum -energy crossing point (MECP) calculation. The meso -pentafluorophenyl group of Mn^ⅤO corrole can change the electrophilicity of the manganese atom and increase electrostatic repulsion between the substituent and the oxygen atom, leading to the improvement of oxygen transferability of Mn^ⅤO corrole. With the increase of the pentafluorophenyl group number at the Mn^ⅤO corrole, the reaction energy barrier decreases accordingly. Furthermore, the reaction energy barrier of the triplet state is significantly lower than that of the singlet state pathway, indicating that spin exchange is prone to occur and the reaction proceeds via triplet state pathway. In the OAT reaction pathway, the reactants in singlet state reach to MECP position firstly, and then change to the triplet state with spin over easily. After that, the reactants follow the triplet state pathway with a lower transition state to achieve the product.
- corrole,
- manganese-oxo complex,
- styrene,
- substituent effect,
- oxygen atom transfer reaction,
- minimum-energy crossing point
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