New insights into the mechanism of proton transfer to hydride complexes:: Kinetic and theoretical evidence showing the existence of competitive pathways for protonation of the cluster [W3S4H3(dmpe)3]+ with acids

被引:41
作者
Algarra, AG
Basallote, MG
Feliz, M
Fernandez-Trujillo, MJ
Llusar, R
Safont, VS
机构
[1] Univ Cadiz, Fac Ciencias, Dept Ciencia Mat Ingn Metalurgia & Quim Inorgan, Cadiz 11510, Spain
[2] Univ Jaume 1, Dept Ciencias Expt, Castellon de La Plana, Spain
关键词
cluster compounds; hydride ligands; kinetics; protonation; reaction mechanisms;
D O I
10.1002/chem.200500695
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The reaction of the hydride cluster [W3S4H3(dmpe)(3)](+) (1, dmpe=1,2-bis(dimethylphosphanyl)ethane) with acids (HCl, CF3COOH, HBF4) in CH2Cl2 solution under pseudo-first-order conditions of excess acid occurs with three kinetically distinguishable steps that can be interpreted as corresponding to successive formal substitution processes of the coordinated hydrides by the anion of the acid (HCl, CF3COOH) or the solvent (HBF4). Whereas the rate law for the third step changes with the nature of the acid, the first two kinetic steps always show a second-order dependence on acid concentration. In contrast, a single kinetic step with a first-order dependence with respect to the acid is observed when the experiments are carried out with a deficit of acid. The decrease in the T, values for the hydride NMR signal of I in the presence of added HCl suggests the formation of an adduct with a W-H...H-Cl dihydrogen bond. Theoretical calculations for the reaction with HCl indicate that the kinetic results in CH2Cl2 solution can be interpreted on the basis of a mechanism with two competitive pathways. One of the pathways consists of direct proton transfer within the W-H... H-Cl adduct to form W-Cl and H-2, whereas the other requires the presence of a second HCl molecule to form a W-H...H-Cl...H-Cl adduct that transforms into W-Cl, H-2 and HCl in the rate-determining step. The activation barriers and the structures of the transition states for both pathways were also calculated, and the results indicate that both pathways can be competitive and that the transition states can be described in both cases as a dihydrogen complex hydrogen-bonded to Cl- or HCl2-.
引用
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页码:1413 / 1426
页数:14
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