Juan Li1, Caihong Wu, Qi Zhang, Bo Yan. 1. Department of Chemistry, Jinan University, Huangpu Road West 601, Guangzhou 510632, P. R. China. tchjli@jnu.edu.cn.
Abstract
Density functional theory calculations have been carried out to study the reaction mechanism of the [Fe(III)(F20TPP)Cl] catalyzed C-H amination reaction. The calculations show that the classical three-step mechanism for other metals (Ru, Rh, Ir and Zn), including N2 liberation, C-N bond formation and 1,2-hydrogen shift, does not fit the iron(III)-catalyzed system. After N2 liberation, the favorable reaction pathway for the iron(iii)-catalyzed system is a 1,2-hydrogen shift preceding C-N bond formation, i.e., a H-abstraction/radical rebound mechanism.
Density functional theory calculations have been carried out to study the reaction mechanism of the [Fe(III)(F20TPP)Cl] catalyzed C-H amination reaction. The calculations show that the classical three-step mechanism for other metals (Ru, Rh, Ir and n class="Chemical">Zn), including N2 liberation, C-N bond formation and 1,2-hydrogen shift, does not fit the iron(III)-catalyzed system. After N2 liberation, the favorable reaction pathway for the iron(iii)-catalyzed system is a 1,2-hydrogen shift preceding C-N bond formation, i.e., a H-abstraction/radical rebound mechanism.