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Dispersion, Rehybridization, and Pentacoordination: Keys to Understand Clustering of Boron and Aluminum Hydrides and Halides

[Image: see text] The structure, stability, and bonding characteristics of dimers and trimers involving BX(3) and AlX(3) (X = H, F, Cl) in the gas phase, many of them explored for the first time, were investigated using different DFT (B3LYP, B3LYP/D3BJ, and M06-2X) and ab initio (MP2 and G4) methods...

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Autores principales: Mó, Otilia, Montero-Campillo, M. Merced, Yáñez, Manuel, Alkorta, Ibon, Elguero, José
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2023
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10364081/
https://www.ncbi.nlm.nih.gov/pubmed/37418427
http://dx.doi.org/10.1021/acs.jpca.3c02747
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author Mó, Otilia
Montero-Campillo, M. Merced
Yáñez, Manuel
Alkorta, Ibon
Elguero, José
author_facet Mó, Otilia
Montero-Campillo, M. Merced
Yáñez, Manuel
Alkorta, Ibon
Elguero, José
author_sort Mó, Otilia
collection PubMed
description [Image: see text] The structure, stability, and bonding characteristics of dimers and trimers involving BX(3) and AlX(3) (X = H, F, Cl) in the gas phase, many of them explored for the first time, were investigated using different DFT (B3LYP, B3LYP/D3BJ, and M06-2X) and ab initio (MP2 and G4) methods together with different energy decomposition formalisms, namely, many-body interaction-energy and localized molecular orbital energy decomposition analysis. The electron density of the clusters investigated was analyzed with QTAIM, electron localization function, NCIPLOT, and adaptive natural density partitioning approaches. Our results for triel hydride dimers and Al(2)X(6) (X = F, Cl) clusters are in good agreement with previous studies in the literature, but in contrast with the general accepted idea that B(2)F(6) and B(2)Cl(6) do not exist, we have found that they are predicted to be weakly bound systems if dispersion interactions are conveniently accounted for in the theoretical schemes used. Dispersion interactions are also dominant in both homo- and heterotrimers involving boron halide monomers. Surprisingly, B(3)F(9) and B(3)Cl(9)C(3v) cyclic trimers, in spite of exhibiting rather strong B–X (X = F, Cl) interactions, were found to be unstable with respect to the isolated monomers due to the high energetic cost of the rehybridization of the B atom, which is larger than the two- and three-body stabilization contributions when the cyclic is formed. Another important feature is the enhanced stability of both homo- and heterotrimers in which Al is the central atom because Al is systematically pentacoordinated, whereas this is not the case when the central atom is B, which is only tri- or tetra-coordinated.
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spelling pubmed-103640812023-07-25 Dispersion, Rehybridization, and Pentacoordination: Keys to Understand Clustering of Boron and Aluminum Hydrides and Halides Mó, Otilia Montero-Campillo, M. Merced Yáñez, Manuel Alkorta, Ibon Elguero, José J Phys Chem A [Image: see text] The structure, stability, and bonding characteristics of dimers and trimers involving BX(3) and AlX(3) (X = H, F, Cl) in the gas phase, many of them explored for the first time, were investigated using different DFT (B3LYP, B3LYP/D3BJ, and M06-2X) and ab initio (MP2 and G4) methods together with different energy decomposition formalisms, namely, many-body interaction-energy and localized molecular orbital energy decomposition analysis. The electron density of the clusters investigated was analyzed with QTAIM, electron localization function, NCIPLOT, and adaptive natural density partitioning approaches. Our results for triel hydride dimers and Al(2)X(6) (X = F, Cl) clusters are in good agreement with previous studies in the literature, but in contrast with the general accepted idea that B(2)F(6) and B(2)Cl(6) do not exist, we have found that they are predicted to be weakly bound systems if dispersion interactions are conveniently accounted for in the theoretical schemes used. Dispersion interactions are also dominant in both homo- and heterotrimers involving boron halide monomers. Surprisingly, B(3)F(9) and B(3)Cl(9)C(3v) cyclic trimers, in spite of exhibiting rather strong B–X (X = F, Cl) interactions, were found to be unstable with respect to the isolated monomers due to the high energetic cost of the rehybridization of the B atom, which is larger than the two- and three-body stabilization contributions when the cyclic is formed. Another important feature is the enhanced stability of both homo- and heterotrimers in which Al is the central atom because Al is systematically pentacoordinated, whereas this is not the case when the central atom is B, which is only tri- or tetra-coordinated. American Chemical Society 2023-07-07 /pmc/articles/PMC10364081/ /pubmed/37418427 http://dx.doi.org/10.1021/acs.jpca.3c02747 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Mó, Otilia
Montero-Campillo, M. Merced
Yáñez, Manuel
Alkorta, Ibon
Elguero, José
Dispersion, Rehybridization, and Pentacoordination: Keys to Understand Clustering of Boron and Aluminum Hydrides and Halides
title Dispersion, Rehybridization, and Pentacoordination: Keys to Understand Clustering of Boron and Aluminum Hydrides and Halides
title_full Dispersion, Rehybridization, and Pentacoordination: Keys to Understand Clustering of Boron and Aluminum Hydrides and Halides
title_fullStr Dispersion, Rehybridization, and Pentacoordination: Keys to Understand Clustering of Boron and Aluminum Hydrides and Halides
title_full_unstemmed Dispersion, Rehybridization, and Pentacoordination: Keys to Understand Clustering of Boron and Aluminum Hydrides and Halides
title_short Dispersion, Rehybridization, and Pentacoordination: Keys to Understand Clustering of Boron and Aluminum Hydrides and Halides
title_sort dispersion, rehybridization, and pentacoordination: keys to understand clustering of boron and aluminum hydrides and halides
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10364081/
https://www.ncbi.nlm.nih.gov/pubmed/37418427
http://dx.doi.org/10.1021/acs.jpca.3c02747
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