A comparative study on the reaction mechanisms of Cp2MH2 (M = Cr, Mo, W) with HBF4

被引：5

作者：

Xu, Xia ^{[1
]}

Sun, Zheng ^{[1
]}

Meng, Lingpeng ^{[1
,2
]}

Zheng, Shijun ^{[1
]}

Li, Xiaoyan ^{[1
,2
]}

机构：

[1] Hebei Normal Univ, Coll Chem & Mat Sci, Rd East 2nd Ring South, Shijiazhuang 050024, Hebei, Peoples R China

[2] Hebei Normal Univ, Natl Demonstratin Ctr Expt Chem, Rd East 2nd Ring South, Shijiazhuang 050024, Hebei, Peoples R China

来源：

APPLIED ORGANOMETALLIC CHEMISTRY | 2019年 / 33卷 / 03期

基金：

中国国家自然科学基金;

关键词：

HBF4; reaction mechanism; topological analysis of electron density; transition metal dihydride; ELECTRON LOCALIZATION FUNCTION; TRANSITION-METAL; TOPOLOGICAL ANALYSIS; LEWIS BASICITY; DIHYDROGEN; HYDROGEN; COMPLEXES; EXCHANGE; HYDRIDE; BONDS;

D O I：

10.1002/aoc.4790

中图分类号：

O69 [应用化学];

学科分类号：

081704 ;

摘要：

The reaction mechanisms of group 6 transition metal dihydride complexes, Cp2MH2 (M = Cr, Mo, and W), and HBF4 were studied using M06-L density functional theory. The chemical bond changes along the reaction pathway are analyzed by the topological analysis of electron density. The calculated results show that the interactions between the H atom of HBF4 and Cp2MH2 are stronger than those between Cp2MH2 and BF3; additionally, due to the low energy barriers in the subsequent reaction, all the title reactions can occur easily, and the yield rates of the Cp2MH2 + HBF4 reactions are high. For M = Cr and Mo, the [Cp2MH3](+) in the product Cp2MH3 center dot BF4 is in the nonclassic dihydrogen-hydride form ([Cp2M(eta(2)-H-2)H](+)). [Cp2CrH3](+) and [Cp2MoH3](+)are unstable, and H-2 can be easily liberated from them. For M = W, the final product is Cp2WH3 center dot BF4, and [Cp2WH3](+) is stable in the classic trihydride form.

引用

页数：10

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