Ítem
Ministerio de Ciencia e Innovación (Espanya)
Ministerio de Educación y Ciencia (Espanya) Generalitat de Catalunya. Agència de Gestió d’Ajuts Universitaris i de Recerca |
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Poater i Teixidor, Jordi
Feixas Geronès, Ferran Bickelhaupt, F. Matthias Solà i Puig, Miquel |
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2011 | |
The π-electrons in benzene, the quintessential aromatic molecule, were previously shown to be distortive, i.e., they prefer localized double bonds alternating with single bonds. It is the σ-electrons that force the double bonds to delocalize, leading to a regular, D6h geometry. Herein, we computationally investigate the double-bond localizing or delocalizing propensities of σ- and π-electrons in the archetypal all-metal aromatic cluster Al4 2- and its second- and fourth-period analogs B4 2- and Ga4 2-, using Kohn-Sham molecular orbital (MO) theory at BP86/TZ2P in combination with quantitative bond energy decomposition analyses (EDA). We compare the three all-metal aromatic clusters with the structurally related organic species C4H 4 2+, C4H4, and C4H 4 2-. Our analyses reveal that the π-electrons in the group-13 M4 2- molecules have a weak preference for localizing the double bonds. Instead, the σ-electrons enforce the regular D4h equilibrium geometry with delocalized double bonds We thank the following organizations for financial support: the HPC-Europa2 Transnational Access program of the European Union, the Netherlands Organization for Scientific Research (NWO), the Ministerio de Ciencia e Innovacion (MICINN, project numbers CTQ2008-03077/BQU, CTQ200806532/BQU and CTQ2011-23156/BQU), the Catalan Departament d’Innovacio , Universitats i Empresa (DIUE, project number 2009SGR637) and the National Research School Combination - Catalysis (NRSC-C). J. P. thanks the MICINN for the Ramon y Cajal contract. Support for the research of M. S. was received through the ICREA Academia 2009 prize for excellence in research funded by the DIUE of the Generalitat de Catalunya |
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application/pdf | |
http://hdl.handle.net/10256/11388 | |
eng | |
Royal Society of Chemistry (RSC) | |
info:eu-repo/semantics/altIdentifier/doi/10.1039/c1cp22759a info:eu-repo/semantics/altIdentifier/issn/1463-9076 info:eu-repo/semantics/altIdentifier/eissn/1463-9084 info:eu-repo/grantAgreement/MICINN//CTQ2011-23156/ES/AVANCES EN CATALISIS Y AROMATICIDAD/ info:eu-repo/grantAgreement/MICINN//CTQ2008-03077/ES/CLUSTERES METALICOS Y SEMIMETALICOS. ESTUDIOS DE AROMATICIDAD Y REACTIVIDAD/ info:eu-repo/grantAgreement/MICINN//CTQ2008-06532/ES/REACTIVIDAD Y ENLACE QUIMICO EN BIOMEDICINA Y QUIMICA (BIO)INORGANICA/ AGAUR/2009-2014/2009 SGR-637 |
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Tots els drets reservats | |
Aromaticitat (Química)
Aromaticity (Chemistry) Funcional de densitat, Teoria del Density functionals |
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All-metal aromatic clusters M4 2- (M = B, Al, and Ga). Are π-electrons distortive or not? | |
info:eu-repo/semantics/article | |
DUGiDocs |