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A comparative study on the reaction mechanisms of Cp 2 MH 2 (M = Cr, Mo, W) with HBF 4
Author(s) -
Xu Xia,
Sun Zheng,
Meng Lingpeng,
Zheng Shijun,
Li Xiaoyan
Publication year - 2019
Publication title -
applied organometallic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.53
H-Index - 71
eISSN - 1099-0739
pISSN - 0268-2605
DOI - 10.1002/aoc.4790
Subject(s) - chemistry , yield (engineering) , hydride , metal , density functional theory , atom (system on chip) , transition metal , crystallography , stereochemistry , computational chemistry , catalysis , organic chemistry , thermodynamics , physics , computer science , embedded system
The reaction mechanisms of group 6 transition metal dihydride complexes, Cp 2 MH 2 (M = Cr, Mo, and W), and HBF 4 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 HBF 4 and Cp 2 MH 2 are stronger than those between Cp 2 MH 2 and BF 3 ; additionally, due to the low energy barriers in the subsequent reaction, all the title reactions can occur easily, and the yield rates of the Cp 2 MH 2 + HBF 4 reactions are high. For M = Cr and Mo, the [Cp 2 MH 3 ] + in the product Cp 2 MH 3 ·BF 4 is in the nonclassic dihydrogen‐hydride form ([Cp 2 M( η 2 ‐H 2 )H] + ). [Cp 2 CrH 3 ] + and [Cp 2 MoH 3 ] + are unstable, and H 2 can be easily liberated from them. For M = W, the final product is Cp 2 WH 3 ·BF 4 , and [Cp 2 WH 3 ] + is stable in the classic trihydride form.