Chemical Bonding and the Equilibrium Composition of Grignard Reagents in Ethereal Solutions
详细信息 查看全文
- 作者：Andr茅 M. Henriques ; Andr茅 G. H. Barbosa
- 刊名：Journal of Physical Chemistry A
- 出版年：2011
- 出版时间：November 10, 2011
- 年：2011
- 卷：115
- 期：44
- 页码：12259-12270
- 全文大小：982K
- 年卷期：v.115,no.44(November 10, 2011)
- ISSN：1520-5215
文摘
A thorough analysis of the electronic structure and thermodynamic aspects of Grignard reagents and its associated equilibrium composition in ethereal solutions is performed. Considering methylmagnesium halides containing fluorine, chlorine, and bromine, we studied the neutral, charged, and radical species associated with their chemical equilibrium in solution. The ethereal solvents considered, tetrahydrofuran (THF) and ethyl ether (Et2O), were modeled using the polarizable continuum model (PCM) and also by explicit coordination to the Mg atoms in a cluster. The chemical bonding of the species that constitute the Grignard reagent is analyzed in detail with generalized valence bond (GVB) wave functions. Equilibrium constants were calculated with the DFT/M06 functional and GVB wave functions, yielding similar results. According to our calculations and existing kinetic and electrochemical evidence, the species R鈥?/sup>, R鈥?/sup>, 鈥?/sup>MgX, and RMgX2鈥?/sup> must be present in low concentration in the equilibrium. We conclude that depending on the halogen, a different route must be followed to produce the relevant equilibrium species in each case. Chloride and bromide must preferably follow a 鈥渞adical-based鈥?pathway, and fluoride must follow a 鈥渃arbanionic-based鈥?pathway. These different mechanisms are contrasted against the available experimental results and are proven to be consistent with the existing thermodynamic data on the Grignard reagent equilibria.