Chemical Bonding and σ-Aromaticity in Charged Molecular Alloys: [Pd2As14]4− and [Au2Sb14]4− Clusters

Abstract We report a computational study on the structures and bonding of a charged molecular alloy D 2h [Pd2As14]4− (1), as well as a model D 2h [Au2Sb14]4− (2) cluster. Our effort makes use of an array of quantum chemistry tools: canonical molecular orbital analysis, adaptive natural density parti...

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Autores principales:	Xue-Rui You, Lin-Yan Feng, Rui Li, Hua-Jin Zhai
Formato:	article
Lenguaje:	EN
Publicado:	Nature Portfolio 2017
Materias:	Medicine R Science Q
Acceso en línea:	https://doaj.org/article/36230522e84f4fa39c50ea06164f733a
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spelling	oai:doaj.org-article:36230522e84f4fa39c50ea06164f733a2021-12-02T16:07:58ZChemical Bonding and σ-Aromaticity in Charged Molecular Alloys: [Pd2As14]4− and [Au2Sb14]4− Clusters10.1038/s41598-017-00867-52045-2322https://doaj.org/article/36230522e84f4fa39c50ea06164f733a2017-04-01T00:00:00Zhttps://doi.org/10.1038/s41598-017-00867-5https://doaj.org/toc/2045-2322Abstract We report a computational study on the structures and bonding of a charged molecular alloy D 2h [Pd2As14]4− (1), as well as a model D 2h [Au2Sb14]4− (2) cluster. Our effort makes use of an array of quantum chemistry tools: canonical molecular orbital analysis, adaptive natural density partitioning, natural bond orbital analysis, orbital composition analysis, and nucleus independent chemical shift calculations. Both clusters consist of two X7 (X = As, Sb) cages, which are interconnected via a M2 (M = Pd, Au) dumbbell, featuring two distorted square-planar MX4 units. Excluding the Pd/As or Au/Sb lone-pairs, clusters 1 and 2 are 50- and 44-electron systems, respectively, of which 32 electrons are for two-center two-electron (2c-2e) As-As or Sb-Sb σ bonds and an additional 16 electrons in 1 for 2c-2e Pd-As σ bonds. No covalent Pd-Pd or Au-Au bond is present in the systems. Cluster 1 is shown to possess two globally delocalized σ electrons, whereas 2 has two σ sextets (each associated with an AuSb4 fragment). Thus, 1 and 2 conform to the (4n + 2) Hückel rule, for n = 0 and 1, respectively, rendering them σ-aromaticity.Xue-Rui YouLin-Yan FengRui LiHua-Jin ZhaiNature PortfolioarticleMedicineRScienceQENScientific Reports, Vol 7, Iss 1, Pp 1-10 (2017)
institution	DOAJ
collection	DOAJ
language	EN
topic	Medicine R Science Q
spellingShingle	Medicine R Science Q Xue-Rui You Lin-Yan Feng Rui Li Hua-Jin Zhai Chemical Bonding and σ-Aromaticity in Charged Molecular Alloys: [Pd2As14]4− and [Au2Sb14]4− Clusters
description	Abstract We report a computational study on the structures and bonding of a charged molecular alloy D 2h [Pd2As14]4− (1), as well as a model D 2h [Au2Sb14]4− (2) cluster. Our effort makes use of an array of quantum chemistry tools: canonical molecular orbital analysis, adaptive natural density partitioning, natural bond orbital analysis, orbital composition analysis, and nucleus independent chemical shift calculations. Both clusters consist of two X7 (X = As, Sb) cages, which are interconnected via a M2 (M = Pd, Au) dumbbell, featuring two distorted square-planar MX4 units. Excluding the Pd/As or Au/Sb lone-pairs, clusters 1 and 2 are 50- and 44-electron systems, respectively, of which 32 electrons are for two-center two-electron (2c-2e) As-As or Sb-Sb σ bonds and an additional 16 electrons in 1 for 2c-2e Pd-As σ bonds. No covalent Pd-Pd or Au-Au bond is present in the systems. Cluster 1 is shown to possess two globally delocalized σ electrons, whereas 2 has two σ sextets (each associated with an AuSb4 fragment). Thus, 1 and 2 conform to the (4n + 2) Hückel rule, for n = 0 and 1, respectively, rendering them σ-aromaticity.
format	article
author	Xue-Rui You Lin-Yan Feng Rui Li Hua-Jin Zhai
author_facet	Xue-Rui You Lin-Yan Feng Rui Li Hua-Jin Zhai
author_sort	Xue-Rui You
title	Chemical Bonding and σ-Aromaticity in Charged Molecular Alloys: [Pd2As14]4− and [Au2Sb14]4− Clusters
title_short	Chemical Bonding and σ-Aromaticity in Charged Molecular Alloys: [Pd2As14]4− and [Au2Sb14]4− Clusters
title_full	Chemical Bonding and σ-Aromaticity in Charged Molecular Alloys: [Pd2As14]4− and [Au2Sb14]4− Clusters
title_fullStr	Chemical Bonding and σ-Aromaticity in Charged Molecular Alloys: [Pd2As14]4− and [Au2Sb14]4− Clusters
title_full_unstemmed	Chemical Bonding and σ-Aromaticity in Charged Molecular Alloys: [Pd2As14]4− and [Au2Sb14]4− Clusters
title_sort	chemical bonding and σ-aromaticity in charged molecular alloys: [pd2as14]4− and [au2sb14]4− clusters
publisher	Nature Portfolio
publishDate	2017
url	https://doaj.org/article/36230522e84f4fa39c50ea06164f733a
work_keys_str_mv	AT xueruiyou chemicalbondingandsaromaticityinchargedmolecularalloyspd2as144andau2sb144clusters AT linyanfeng chemicalbondingandsaromaticityinchargedmolecularalloyspd2as144andau2sb144clusters AT ruili chemicalbondingandsaromaticityinchargedmolecularalloyspd2as144andau2sb144clusters AT huajinzhai chemicalbondingandsaromaticityinchargedmolecularalloyspd2as144andau2sb144clusters
_version_	1718384647415529472

Chemical Bonding and σ-Aromaticity in Charged Molecular Alloys: [Pd2As14]4− and [Au2Sb14]4− Clusters

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