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

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Abstract

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.

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Authors and Affiliations

  1. Chemistry Research Institute, N. I. Lobachevsky State University of Nizhny Novgorod, Bldg. 5, 23 prosp. Gagarina, 603600, Nizhny Novgorod, Russian Federation

    S. V. Panteleev, S. K. Ignatov & S. V. Maslennikov

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  1. S. V. Panteleev
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  2. S. K. Ignatov
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  3. S. V. Maslennikov
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Correspondence to S. K. Ignatov.

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Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 458–469, March, 2008.

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Panteleev, S.V., Ignatov, S.K. & Maslennikov, S.V. Adsorption of solvent and oxidant molecules on magnesium surface: effect on the electronic structure and reactivity of magnesium in reactions of Grignard reagent formation. Russ Chem Bull 57, 468–479 (2008). https://doi.org/10.1007/s11172-008-0074-z

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