A new look at the chalcogen bond: π-hole-based chalcogen (Se, Te) bonding which does not include a σ-hole interaction

A new look at the chalcogen bond: π-hole-based chalcogen (Se, Te) bonding which does not include a σ-hole interaction Full article

Journal

Inorganic Chemistry Frontiers
ISSN: 2052-1553

Output data

Year: 2023, Volume: 10, Number: 10, Pages: 3065-3081 Pages count : 17 DOI: 10.1039/d3qi00087g

Authors

Katlenok Eugene A. ¹ , Kuznetsov Maxim L. ² , Semenov Nikolay A. ³ , Bokach Nadezhda A. ¹ , Kukushkin Vadim Yu. ^1,2

Affiliations

1	Saint Petersburg State University
2	Centro de Química Estrutural, Institute of Molecular Sciences, Departamento de Engenharia Química, Instituto Superior Técnico, Universidade de Lisboa
3	N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry of Siberian Branch of Russian Academy of Sciences

The solid-state structures of co-crystals of chalcogenadiazoles (ChDAs) with planar half-lantern PtII2 and mononuclear PtII complexes exhibit short Ch⋯PtII (Ch = Se, Te) contacts that occur between a metal site and the ChDA. The structures demonstrate a unique geometric feature whereby the two deep σ-holes of ChDA are turned away from a dz2-nucleophilic PtII site. A comprehensive DFT study (PBE0-D3BJ; computational tools QTAIM, ELF, IGMH, MEP, CDF, ETS-NOCV, and SAPT), focused on the analysis of these puzzling structural features, revealed that a platinum(II) center does not interact with the deep σ-holes of ChDA but is involved in other types of interactions including, in particular, with a π-hole at the Ch site. The unusual linkage between a platinum(II) atom and ChDA is driven by the combined action of the Pt → π-hole on Ch bonding (30–41% of the total interaction energy) and other C⋯C/C⋯S π-hole interactions involving the ChDA and ligand's arenes. The effect of the combined action of these interactions is so expressed that the Ch⋯Pt interaction structurally mimics a semicoordination bond. However, significant dz2(Pt) → π*(ChDA) charge transfer allows the assignment of the Ch⋯Pt interactions to the chalcogen bonding.

Katlenok E.A. , Kuznetsov M.L. , Semenov N.A. , Bokach N.A. , Kukushkin V.Y.
A new look at the chalcogen bond: π-hole-based chalcogen (Se, Te) bonding which does not include a σ-hole interaction
Inorganic Chemistry Frontiers. 2023. V.10. N10. P.3065-3081. DOI: 10.1039/d3qi00087g WOS РИНЦ OpenAlex

Accepted:	Mar 30, 2023
Published print:	Apr 1, 2023

Web of science:	WOS:000975290400001
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OpenAlex:	W4362162930

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