Significant bonding rearrangements triggered by Mg₄ clusters

The structure, stability, and bonding of the complexes formed by the interaction of Mg₄ clusters and first row Lewis bases, namely, ammonia, water, and hydrogen fluoride, have been investigated through the use of high-level G4 single-reference and CASPT2 multireference formalisms. The adducts formed reflect the high electrophilicity of the Mg₄ cluster through electron density holes in the neighborhood of each metallic center. After the adduct formation, the metallic bonding of the Mg₄ moiety is not significantly altered so that the hydrogen shifts from the Lewis base toward the Mg atoms lead to new local minima with enhanced stability. For the particular case of ammonia and water, the global minima obtained when all the hydrogens of the Lewis base are shifted to the Mg₄ moiety have in common a very stable scaffold with a N or an O center covalently tetracoordinated to the four Mg atoms, so the initial bonding arrangements of both reactants have completely disappeared. The reactivity features exhibited by these Mg₄ clusters suggest that nanostructures of this metal might have an interesting catalytic behavior.