Planar pentacoordinate s-block metals
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Fecha
2023-07
Profesor/a Guía
Facultad/escuela
Idioma
en
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ISSN de la revista
Título del volumen
Editor
Royal Society of Chemistry
Nombre de Curso
Licencia CC
Attribution-NonCommercial 3.0 Unported Deed (CC BY-NC 3.0 )
Licencia CC
https://creativecommons.org/licenses/by-nc/3.0/
Resumen
The presence of a delocalized π-bond is often considered an essential criterion for achieving planar hypercoordination. Herein, we show that σ-delocalization could be sufficient to make the planar configuration the most stable isomer in a series of planar pentacoordinate s-block metals. High-level ab initio computations reveal that the global minimum of a series of interalkali and interalkali-alkaline earth clusters (LiNa5, Li5Mg+, Na5Mg+, K5Ca+, CaRb5+, Rb5Sr+, and SrCs5+) adopts a singlet D5h structure with a planar pentacoordinate lithium or alkaline earth metal (AE = Mg, Ca, Sr). These clusters are unusual combinations to stabilize a planar pentacoordinate atom, as all their constituents are electropositive. Despite the absence of π-electrons, Hückel's rule is fulfilled by the six σ-electrons. Furthermore, the systems exhibit a diatropic ring current in response to an external magnetic field and a strong magnetic shielding, so they might be classified as σ-aromatic. Therefore, multicenter σ-bonds and the resulting σ-delocalization stabilize these clusters, even though they lack π-aromaticity. © 2023 The Royal Society of Chemistry.
https://pubs.rsc.org/en/content/articlelanding/2023/sc/d2sc05939h
https://pubs.rsc.org/en/content/articlelanding/2023/sc/d2sc05939h
Notas
Indexación: Scopus
Palabras clave
Ab initio Computations, Alkaline Earth, Alkaline-earth Metals, Global Minimum, Hypercoordination, Planar Configurations, S-block Metals, Stable Isomers, π-electrons, σ-delocalization
Citación
Chemical Science. Volume 14, Issue 33, Pages 8785 - 879114. July 2023
DOI
10.1039/d2sc05939h