Exploring the reaction mechanism of a cationic terminal iridium methylene complex with ethyl diazoacetate, a Lewis base and dihydrogen: a quantum chemistry study

被引：4

作者：

Ye, Xinchen ^{[1
]}

Yang, Liu ^{[1
]}

Wu, Zunyi ^{[1
]}

Ren, Gerui ^{[1
]}

Lu, Yanbin ^{[1
]}

Sun, Tingting ^{[2
]}

Lei, Qunfang ^{[3
]}

Fang, Wenjun ^{[3
]}

Xie, Hujun ^{[1
]}

机构：

[1] Zhejiang Gongshang Univ, Dept Appl Chem, Sch Food Sci & Biotechnol, Hangzhou 310035, Zhejiang, Peoples R China

[2] Zhejiang Gongshang Univ, Dept Phys, Sch Informat & Elect Engn, Hangzhou 310018, Zhejiang, Peoples R China

[3] Zhejiang Univ, Dept Chem, Hangzhou 310027, Zhejiang, Peoples R China

来源：

NEW JOURNAL OF CHEMISTRY | 2014年 / 38卷 / 09期

基金：

中国博士后科学基金; 美国国家科学基金会;

关键词：

POTENTIAL BASIS-SETS; H BOND ACTIVATION; POLARIZATION FUNCTIONS; DENSITY FUNCTIONALS; ENERGIES; ELEMENTS;

D O I：

10.1039/c4nj00757c

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The mechanisms for the formation of a cationic methylene complex [(PONOP)Ir(CH2)](+) (PONOP = 2,6-bis(ditert-butylphosphinito)pyridine) via alpha-hydride abstraction from a neutral methyl complex [(PONOP)Ir(CH3)] and its reactivity with ethyl diazoacetate, a Lewis base (PMe3) and dihydrogen have been studied computationally with the aid of density functional theory (DFT). The calculation results show that the eta(2)-alkene complex can be formed via a direct C-C coupling reaction involving the methylene ligand and ethyl diazoacetate. A ylide compound is given for the reaction of this cationic methylene complex with PMe3. In addition, hydrogenolysis of the Ir=CH2 moiety of this cationic methylene complex results in a hydride iridium complex. Our calculations could provide new insights into the reactivity of methylene complexes.

引用

页码：4115 / 4119

页数：5