Systematic quantum chemical research of the reaction of magnesium clusters with organic halides

► We computationally studied the interaction between magnesium clusters and organic halides. ► We found four reaction channels that can be classified as radical and non-radical. ► Calculated Gibbs free energies of activation are close to experimental values. ► For alkyl chlorides, radical channels are preferred. ► Regarding vinyl and phenyl halides, radical channels are only preferred due to the entropy factor.