TY - JOUR

T1 - Inorganic–Organic {dz2-MIIS4}···π-Hole Stacking in Reverse Sandwich Structures. The Case of Cocrystals of Group 10 Metal Dithiocarbamates with Electron-deficient Arenes.

AU - Zelenkov, Lev E.

AU - Eliseeva, Anastasiya A.

AU - Baykov, Sergey

AU - Ivanov, Daniil M.

AU - Sumina, Alina I.

AU - Gomila, Rosa

AU - Frontera, Antonio

AU - Kukushkin, Vadim Yu.

AU - Bokach , Nadezhda A.

N1 - Publisher Copyright: © 2022 The Royal Society of Chemistry

PY - 2022/4/19

Y1 - 2022/4/19

N2 - Cocrystallization of the dithiocarbamate complexes [M(S 2CNEt 2) 2] (M = Ni 1, Pd 2, Pt 3) and X-substituted perfluoroarenes (X = I, Br; 1,2-dibromoperfluorobenzene FBrB and 1,2-diiodoperfluorobenzene FIB) gives isomorphous cocrystals of (1-3)·2(FBrB) and 1·2(FIB), correspondingly, whose structures were studied by single-crystal X-ray diffractometry. The crystal structures demonstrate similar intermolecular contact types: short arene MS 4⋯π-hole stacking contacts, X⋯S halogen bonds, C-H⋯X (X = Br, I) bonds and C-H⋯F hydrogen bonds. In these structures, the {d z 2 -M IIS 4} moiety functions as an integrated five-center acceptor (that includes a metal d z 2 -orbital, even for a poorly d z 2 -nucleophilic Ni II center) toward the π-hole of an X-substituted perfluoroarene. This interaction provides stacking of inorganic and organic units furnishing the reverse sandwich structures. Density functional theory (DFT) calculations, in combination with quantum theory of atoms-in-molecules (QTAIM) and noncovalent interaction plot (NCIplot) analyses, supported the structure-defining role of the {MS 4}⋯π-hole contacts. The nucleophilicity of the {MS 4} cores toward electron deficient π-holes was verified from the molecular electrostatic potential surface (MEP) and electron density/electrostatic potential (ED/ESP) profiles, and atoms-in-molecules (AIM) charge analysis. The relatively strong {MS 4}⋯π-hole contact strength (interaction energies for an {MS 4}⋯π-hole 1 : 1 adduct range from −12.1 to −13.5 kcal mol −1) is probably due to the large overlap between the electron deficient π-cloud and the integrated {MS 4} nucleophilic core. The 1 : 1 adduct based on 3 demonstrates the largest strength (13.5 kcal mol −1) in the series and this strength agrees well with the higher d z 2 -nucleophilicity of the Pt II center revealed by the MEP analysis (−33.6 kcal mol −1).

AB - Cocrystallization of the dithiocarbamate complexes [M(S 2CNEt 2) 2] (M = Ni 1, Pd 2, Pt 3) and X-substituted perfluoroarenes (X = I, Br; 1,2-dibromoperfluorobenzene FBrB and 1,2-diiodoperfluorobenzene FIB) gives isomorphous cocrystals of (1-3)·2(FBrB) and 1·2(FIB), correspondingly, whose structures were studied by single-crystal X-ray diffractometry. The crystal structures demonstrate similar intermolecular contact types: short arene MS 4⋯π-hole stacking contacts, X⋯S halogen bonds, C-H⋯X (X = Br, I) bonds and C-H⋯F hydrogen bonds. In these structures, the {d z 2 -M IIS 4} moiety functions as an integrated five-center acceptor (that includes a metal d z 2 -orbital, even for a poorly d z 2 -nucleophilic Ni II center) toward the π-hole of an X-substituted perfluoroarene. This interaction provides stacking of inorganic and organic units furnishing the reverse sandwich structures. Density functional theory (DFT) calculations, in combination with quantum theory of atoms-in-molecules (QTAIM) and noncovalent interaction plot (NCIplot) analyses, supported the structure-defining role of the {MS 4}⋯π-hole contacts. The nucleophilicity of the {MS 4} cores toward electron deficient π-holes was verified from the molecular electrostatic potential surface (MEP) and electron density/electrostatic potential (ED/ESP) profiles, and atoms-in-molecules (AIM) charge analysis. The relatively strong {MS 4}⋯π-hole contact strength (interaction energies for an {MS 4}⋯π-hole 1 : 1 adduct range from −12.1 to −13.5 kcal mol −1) is probably due to the large overlap between the electron deficient π-cloud and the integrated {MS 4} nucleophilic core. The 1 : 1 adduct based on 3 demonstrates the largest strength (13.5 kcal mol −1) in the series and this strength agrees well with the higher d z 2 -nucleophilicity of the Pt II center revealed by the MEP analysis (−33.6 kcal mol −1).

UR - https://www.mendeley.com/catalogue/86efdbc5-2d38-3c20-b186-d07c25f137d4/

UR - http://www.scopus.com/inward/record.url?scp=85133597782&partnerID=8YFLogxK

U2 - 10.1039/D2QI00438K

DO - 10.1039/D2QI00438K

M3 - Article

VL - 9

SP - 2869

EP - 2879

JO - Inorganic Chemistry Frontiers

JF - Inorganic Chemistry Frontiers

SN - 2052-1545

IS - 12

ER -