Metal-involved C⋯dz2-PtII tetrel bonding as a principal component of the stacking interaction between arenes and the platinum(ii) square-plane

• Published in: Inorganic chemistry frontiers 2023-06, Vol.10 (13), p.3916-3928
• Main Authors: Katlenok, Eugene A, Kuznetsov, Maxim L, Cherkasov, Anton V, Kryukov, Dmitry M, Bokach, Nadezhda A, Vadim Yu Kukushkin
• Format: Article
• Language: English
• Subjects: Aromatic compounds; Charge transfer; Crystallization; Crystallography; Density functional theory; Inorganic chemistry; Many body problem; Software; Stacking
• ISSN: 2052-1545; 2052-1553
• DOI: 10.1039/d3qi00555k

The half-lantern Pt2II complexes [Pt(C∩N)(μ-S∩N)]2 (C∩N = 2-naphtylbenzothiazolate 1; 2-phenylbenzothiazolate 2; S∩N = 2-thiopyridine) were crystallized with electron-deficient arenes such as hexafluorobenzene (C6F6) and octafluoroanthraquinone (OFA) to furnish cocrystals 1·C6F6, 2·C6F6, and 1·(OFA)2, all studied by X-ray crystallography. The obtained structural data revealed that structure-determining π–π stacking occurred between the arenes and metal square-planes. Density functional theory calculations, employing a set of computational tools, verified the contribution of the C⋯dz2-PtII noncovalent bond in the overall stacking forces. Orbital interaction analysis using the charge displacement function (CDF) combined with the extended transition state natural orbital for chemical valence theory (ETS-NOCV) method demonstrated the significance of the dz2(Pt) → π*(C) charge-transfer interaction, which allows the attribution of the C⋯Pt contact to a metal-involved tetrel bonding. Many-body interaction analysis demonstrates a positive cooperative effect between the fragments of the half-lantern complex and the perfluoroarenes favoring the occurrence of supramolecular chains.