A combined experimental and computational study on the reaction of fluoroarenes with Mg-Mg, Mg-Zn, Mg-Al and Al-Zn bonds.

ABSTRACT: Through a combined experimental and computational (DFT) approach, the reaction mechanism of the addition of fluoroarenes to Mg-Mg bonds has been determined as a concerted S_NAr-like pathway in which one Mg centre acts as a nucleophile and the other an electrophile. The experimentally determined Gibbs activation energy for the addition of C₆F₆ to a Mg-Mg bond of a molecular complex, ΔG‡298 K(experiment) = 21.3 kcal mol^-1 is modelled by DFT with the ωB97X functional, ΔG‡298 K(DFT) = 25.7 kcal mol^-1. The transition state for C-F activation involves a polarisation of the Mg-Mg bond and significant negative charge localisation on the fluoroarene moiety. This transition state is augmented by stabilising closed-shell Mg···F

SUBMITTER: Bakewell C 

PROVIDER: S-EPMC5897846 | biostudies-literature | 2018 Feb

REPOSITORIES: biostudies-literature