Determining the inherent selectivity for carbon radical hydroxylation versus halogenation with high-spin oxoiron(iv)-halide complexes: a concerted rebound step

Yaping Tao; Zixian Li; Yiman Zhang; Kexi Sun; Zhaojun Liu

doi:10.1039/d2ra01384c

Determining the inherent selectivity for carbon radical hydroxylation versus halogenation with high-spin oxoiron(iv)-halide complexes: a concerted rebound step

RSC Adv. 2022 Mar 29;12(16):9891-9897. doi: 10.1039/d2ra01384c. eCollection 2022 Mar 25.

Authors

Yaping Tao¹, Zixian Li², Yiman Zhang¹, Kexi Sun¹, Zhaojun Liu¹

Affiliations

¹ College of Physics and Electronic Information & Henan Key Laboratory of Electromagnetic Transformation and Detection, Luoyang Normal University Luoyang 471934 China zhaojunliu@gmail.com.
² State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology Beijing 100029 China.

Abstract

A synthetic iron model can process both halogenation and hydroxylation with vague selectivity, which is different from halogenase even though these structures are used for the simulation of halogenase. The key factor of the synthetic oxo-iron model mediated hydroxylation or the halogenation is still under debate. Herein density functional theory calculation is used to investigate the hydroxylation versus halogenation of propylene by the complex [Fe^IV(O)(TQA)(X)]⁺ (X = F, Cl, Br). Our results suggest that a concerted rebound mechanism (between the -X and the hydroxyl ligands after the hydrogen abstraction) leads to the formation of two different kinds of products.