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

The solid-state structures of co-crystals of chalcogenadiazoles (ChDAs) with planar half-lantern Pt2II 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...

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Bibliographic Details
Published in:Inorganic chemistry frontiers 2023-05, Vol.10 (10), p.3065-3081
Main Authors: Katlenok, Eugene A, Kuznetsov, Maxim L, Semenov, Nikolay A, Bokach, Nadezhda A, Vadim Yu Kukushkin
Format: Article
Language:English
Subjects:
Aromatic compounds
Bonding
Chalcogen bonds
Charge transfer
Inorganic chemistry
Platinum
Software
Tellurium
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Summary:The solid-state structures of co-crystals of chalcogenadiazoles (ChDAs) with planar half-lantern Pt2II 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.
ISSN:2052-1545
2052-1553
DOI:10.1039/d3qi00087g