TY - JOUR

T1 - Metal-involved C···dz2-PtII tetrel bonding as a principal component of the stacking interaction between arenes and the platinum(II) square-plane

AU - Катленок, Евгений Анатольевич

AU - Кузнецов, Максим Леонидович

AU - Черкасов, Антон

AU - Крюков, Дмитрий Михайлович

AU - Бокач, Надежда Арсеньевна

AU - Кукушкин, Вадим Юрьевич

PY - 2023

Y1 - 2023

N2 - π–π stacking which includes metal-involved C⋯d z 2 -Pt II tetrel bonding. The half-lantern PtII2 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 (C 6 F 6 ) and octafluoroanthraquinone (OFA) to furnish cocrystals 1·C 6 F 6 , 2·C 6 F 6 , 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⋯d z 2 -Pt II 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 d z 2 (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.

AB - π–π stacking which includes metal-involved C⋯d z 2 -Pt II tetrel bonding. The half-lantern PtII2 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 (C 6 F 6 ) and octafluoroanthraquinone (OFA) to furnish cocrystals 1·C 6 F 6 , 2·C 6 F 6 , 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⋯d z 2 -Pt II 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 d z 2 (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.

UR - https://www.mendeley.com/catalogue/b037e099-2a96-3126-b558-b61e9bea1e10/

U2 - 10.1039/D3QI00555K

DO - 10.1039/D3QI00555K

M3 - Article

VL - 10

SP - 3916

EP - 3928

JO - Inorganic Chemistry Frontiers

JF - Inorganic Chemistry Frontiers

SN - 2052-1545

IS - 13

ER -