A computational study solves an old chemical mystery

In their publication The Grignard Reaction - Unraveling a Chemical Puzzle, Hylleraas members Raphael M. Peltzer, Michele Cascella and Odile Eisenstein, in collaboration with Jürgen Gauss  (Uni. Mainz), solve the old chemical puzzle of the Grignard reaction

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The mechanism of the Grignard reaction has eluded the comprehension of chemists for more than 100 years, but thanks to a combination of ab initio molecular dynamics and quantum chemistry calculations, this riddle is now deciphered. The complexity of the Grignard reaction is due to both the existence of multiple organomagnesium species in solution, and the possible competition between the nucleophilic addition and the radical mechanisms. 

In this study, the reactivity of all species at equilibrium has been characterised, demonstrating that several of them are competent. Dialkylmagnesium and a dinuclear complex were identified as the most reactive ones. The radical pathway is strictly controlled by the nature of the substrate through coordination to the Mg atom. In all cases, the solvent is an essential actor in the reaction. This study was conducted at the Hylleraas Centre by Raphael M. Peltzer as part of his PhD, under the supervision of Michele Cascella and Odile Eisenstein, in collaboration with Jürgen Gauss (Uni. Mainz).

Published Jan. 22, 2020 4:25 PM - Last modified Jan. 22, 2020 4:48 PM