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On closed-shell interactions between heavy main-group elements
KTH, School of Chemical Science and Engineering (CHE), Centres, Centre of Molecular Devices, CMD. KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemistry, Applied Physical Chemistry.ORCID iD: 0000-0002-0168-2942
2022 (English)In: Journal of Computational Chemistry, ISSN 0192-8651, E-ISSN 1096-987X, Vol. 43, no 29, p. 1985-1996Article in journal (Refereed) Published
Abstract [en]

A series of di- and polymetal complexes involving closed-shell, heavy main-group atoms and ions shows a selection of special physical properties. These involve short metal-metal contacts, low entropies of formation and, most interestingly, strong Raman bands at low wavenumbers. These results together with the constitution of the coordination compounds, where the majority of electrons are assembled on the highly polarizable metal atoms and ions, experimental results have been interpreted in terms of direct, partial covalent metal-metal bonding. Previous theoretical studies have challenged this view and instead attributed the obvious attractive forces involved to secondary-type of interactions, such as dispersion. This study utilizes a multitude of theoretical tools, such as natural bond order (NBO) and natural energy decomposition analysis (NEDA), non-covalent interaction (NCI) analysis, electron localization functions (ELFs), and atoms-in-molecules (AIM) to characterize the interactions in models comprising closed-shell dimers, as well as experimentally studied ring and cage systems constituting the main reason for the hypotheses on metal-metal interactions. The results show that all experimental results can be attributed to the covalent interactions between the electron-rich, metal centers and the bridging anions in ring and cage coordination compounds of high symmetry, where the experimentally observed effects can be traced to the combination of covalent interactions between the metal centers and the anions along the edges of the ring and cage systems in combination with the cooperative effects generated by the high symmetry of these ring and cage systems.

Place, publisher, year, edition, pages
Wiley , 2022. Vol. 43, no 29, p. 1985-1996
Keywords [en]
closed-shell interaction, covalent interaction, intermolecular interactions, main-group elements
National Category
Physical Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-319708DOI: 10.1002/jcc.26999ISI: 000857932900001PubMedID: 36129213Scopus ID: 2-s2.0-85138419242OAI: oai:DiVA.org:kth-319708DiVA, id: diva2:1706201
Note

QC 20221025

Available from: 2022-10-25 Created: 2022-10-25 Last updated: 2022-10-25Bibliographically approved

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Kloo, Lars

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