Significant bonding rearrangements triggered by Mg4 clusters
| Autor: | M. Merced Montero-Campillo, Otilia Mó, Eva Vos, Inés Corral |
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| Přispěvatelé: | UAM. Departamento de Química |
| Jazyk: | angličtina |
| Rok vydání: | 2021 |
| Předmět: |
Hydrogen
Hydrogen shifts General Physics and Astronomy chemistry.chemical_element Adduct formation 010402 general chemistry 01 natural sciences Adduct Enhanced stability Ammonia 0103 physical sciences Cluster (physics) Moiety Fluorine compounds Magnesium Lewis acids and bases Physical and Theoretical Chemistry Electrophilicity Hydrogen fluoride Metallic centers Scaffolds 010304 chemical physics Química 0104 chemical sciences Crystallography chemistry Covalent bond Catalytic behavior Electrophile Metallic bonding |
| Zdroj: | Biblos-e Archivo. Repositorio Institucional de la UAM Universitat Autònoma de Barcelona |
| Popis: | This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. This article appeared in Journal of Chemical Physics 154.4 (2021): 044302 and may be found at https://doi.org/10.1063/5.0038047 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 This work was supported by the projects PGC2018-094644-BC21, PGC2018-094644-B-C22, and PID2019-110091GB-I00 (MICINN) of the Ministerio de Ciencia, Innovación y Universidades of Spain |
| Databáze: | OpenAIRE |
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