Adsorption of solvent and oxidant molecules on magnesium surface: effect on the electronic structure and reactivity of magnesium in reactions of Grignard reagent formation

The effect of adsorption of the oxidant (EtBr) and aprotic dipolar solvent molecules on the electronic structure and properties of Mg _n (n ≤ 50) clusters simulating the surface of metallic magnesium was studied by the B3PW91/6-31G(d) density functional method. It was found that the work function of an electron from the cluster monotonically decreases as the donor ability of the adsorbed molecules increases. The experimentally measured rate of the magnesium oxidation by EtBr correlates with the negative Mulliken charge density of the first coordination sphere of the surface adsorption site. The results obtained are in agreement with the experimentally determined work function of electron from metals during adsorption from the gas phase. Presumably, the rate-limiting step of the Grignard reagent formation is the surface oxidation reaction. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 458–469, March, 2008.