Zhang Xinghui, Wu Xi, Lei Yun
College of Chemical Engineering, Lanzhou University of Arts and Science, Lanzhou, 730010, Gansu, People's Republic of China.
School of Foreign Languages, Lanzhou University of Arts and Science, Lanzhou, 730010, Gansu, People's Republic of China.
J Mol Model. 2019 Aug 17;25(9):261. doi: 10.1007/s00894-019-4145-x.
DFT calculations at the M06-2X level were performed to explore the reaction mechanism for the synthesis of the new cyclometalated iridium(III) complexes with acyclic diaminocarbene ancillary ligands. The solvent effects of the reaction systems have been considered by a single-point energy calculation using the SMD model in the experimental conditions of CHCl solvent. The calculated results show that the reaction consists of two main steps: the first step is the hydrogen transfer between the two N atoms, and the next step is the closed-loop process of the Ir atom and the aromatic ring ortho to release the HCl molecule. The reaction has a relatively low activation free energy of 17.1-23.2 kcal mol, indicating that it is easy to occur under the experimental conditions of Na et al. At the same time, it was found that the aryl para-CF substituent has higher reactivity than the corresponding reactant of the NO substituent.
在M06 - 2X水平上进行密度泛函理论（DFT）计算，以探究用无环二氨基卡宾辅助配体合成新型环金属化铱（III）配合物的反应机理。在CHCl溶剂的实验条件下，通过使用SMD模型的单点能量计算来考虑反应体系的溶剂效应。计算结果表明，该反应包括两个主要步骤：第一步是两个N原子之间的氢转移，下一步是Ir原子与芳环邻位的闭环过程并释放HCl分子。该反应具有相对较低的活化自由能，为17.1 - 23.2千卡/摩尔，表明在Na等人的实验条件下很容易发生。同时，发现芳基对位-CF取代基比相应的NO取代基反应物具有更高的反应活性。
