文献类型：期刊文献

英文题名：Theoretical investigation of mechanism and ligand effects on half-sandwich iridium complexes for direct reductive amination

作者：Wang, Jingyi[1];Liu, Chengyu[2];Cao, Liming[2];Xiong, Yan[1];Ye, Jinxing[3];Liu, Zhen[1];Cheng, Ruihua[1,3]

机构：[1]East China Univ Sci & Technol, Sch Chem Engn, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Engn Res Ctr Pharmaceut Proc Chem, Sch Pharm, Minist Educ, Shanghai 200237, Peoples R China;[3]Guangdong Univ Technol, Sch Biomed & Pharmaceut Sci, Guangzhou 510006, Peoples R China

年份：2022

卷号：517

外文期刊名：MOLECULAR CATALYSIS

收录：;EI(收录号：20215111355619);WOS:【SCI-EXPANDED(收录号:WOS:000737842500002)】；

基金：We thank the financial support of the National Natural Science Foundation of China (22071056).

语种：英文

外文关键词：Half-sandwich iridium complexes; Reductive amination; Ligand effect; Density function theory

摘要：The reaction mechanisms of direct reductive amination catalyzed by half-sandwich Cp*Ir complexes and the possible side reactions - transfer hydrogenation of ketones and N-formylation of amines have been explored by density functional theory (DFT). The reaction involves two steps: (1) the hydridoiridium formation as a ratedetermining step, and (2) the hydride transfer to obtain amines. The relationships between the structure and activity of Cp*Ir complexes were analyzed by natural population analysis (NPA), Bader's atoms in molecules theory (AIM) and frontier molecular orbital (FMO). In general, the picolinamidato ligands are more favorable than the sulfonamidato ones due to the electronic effect. The catalyst with the phenyl ring bearing functional groups on the N-amide exerts the positive effect on the catalytic activity. Furthermore, the electron-donating group on the pyridine ring provides better performance owing to the higher NPA charge on the Ir atom, the lower electron density at the Ir-Cl bond critical point, and the destabilization of the highest occupied molecular orbital (HOMO).