TY - JOUR

T1 - Halogen Bonding Involving Palladium(II) as an XB Acceptor

AU - Katlenok, Eugene A.

AU - Rozhkov, Anton V.

AU - Levin, Oleg V.

AU - Haukka, Matti

AU - Kuznetsov, Maxim L.

AU - Kukushkin, Vadim Yu

N1 - Funding Information: The synthetic and crystal engineering parts of this work have been supported by the Russian Science Foundation (Grant 20-13-00144), while the electrochemical part, by the Russian Foundation for Basic Research (Grant 19-29-08026), and computational part, by the Fundação para a Ciência e a Tecnologia (FCT), Portugal, through Project UIDB/00100/2020 of Centro de Química Estrutural. E.A.K. thanks Saint Petersburg State University for the postdoctoral fellowship. Physicochemical studies were performed at the Center for Magnetic Resonance, Center for X-ray Diffraction Studies, and Center for Chemical Analysis, Materials Research and Chemistry Educational Centre (all belonging to Saint Petersburg State University). Calculations were performed at Saint Petersburg University Computational Center and at Centro de Química Estrutural. V.Y.K. is grateful to South Ural State University (Act 211 Government of the Russian Federation, Contract No. 02.A03.21.0011) for putting facilities at his disposal. M.L.K. acknowledges FCT and Instituto Superior Técnico for the contract within the CEEC 2018 Institutional Program (Contract No. IST-ID/295/2019). Publisher Copyright: © 2020 American Chemical Society. Copyright: Copyright 2021 Elsevier B.V., All rights reserved.

PY - 2021/2/3

Y1 - 2021/2/3

N2 - The half-lantern PdII2 complexes trans-(O,C)-[Pd(ppz)(μ-O∩N)]2 (1) and trans-(E,N)-[Pd(ppz)(μ-E∩N)]2 (E∩N is a deprotonated 2-substituted pyridine; E = S (2), Se (3); Hppz = 1-phenylpyrazole) were cocrystallized with 1,4-diiodotetrafluorobenzene (FIB) to give cocrystals 1·(FIB) and (2-3)·2(FIB); the parent complexes and the cocrystals were studied by X-ray crystallography. The crystal structure of trans-(O,C)-1·FIB is assembled mainly by the I···O halogen bonding (XB) to give the [@PdII2]O···I(areneF)I···O[@PdII2] linkage, while trans-(E,N)-(2-3)·2(FIB) are built by the joint action of I···Pd and I···E XBs, thus furnishing the PdII2···I(areneF)I···E[@PdII2] (E = S, Se) cluster. Detailed theoretical (DFT) studies with the application of the QTAIM, ELF, NBO, IGM, SAPT, and HSAB methods revealed several types of attractive noncovalent interactions in the cocrystals, namely, the I···Pd, I···E (E = O, S, Se), I···C, π-π-stacking, and π···F interactions. I···Pd is a rare type of XB involving the metal center as an XB acceptor, the Pd···Pd communication facilitating the I···Pd bonding. The I···Pd and I···E bonds are comparable in strength (the bond interaction energies being between -7 and -13 kcal/mol), but the former is controlled by dispersion forces, while the latter is mostly governed by an electrostatic term.

AB - The half-lantern PdII2 complexes trans-(O,C)-[Pd(ppz)(μ-O∩N)]2 (1) and trans-(E,N)-[Pd(ppz)(μ-E∩N)]2 (E∩N is a deprotonated 2-substituted pyridine; E = S (2), Se (3); Hppz = 1-phenylpyrazole) were cocrystallized with 1,4-diiodotetrafluorobenzene (FIB) to give cocrystals 1·(FIB) and (2-3)·2(FIB); the parent complexes and the cocrystals were studied by X-ray crystallography. The crystal structure of trans-(O,C)-1·FIB is assembled mainly by the I···O halogen bonding (XB) to give the [@PdII2]O···I(areneF)I···O[@PdII2] linkage, while trans-(E,N)-(2-3)·2(FIB) are built by the joint action of I···Pd and I···E XBs, thus furnishing the PdII2···I(areneF)I···E[@PdII2] (E = S, Se) cluster. Detailed theoretical (DFT) studies with the application of the QTAIM, ELF, NBO, IGM, SAPT, and HSAB methods revealed several types of attractive noncovalent interactions in the cocrystals, namely, the I···Pd, I···E (E = O, S, Se), I···C, π-π-stacking, and π···F interactions. I···Pd is a rare type of XB involving the metal center as an XB acceptor, the Pd···Pd communication facilitating the I···Pd bonding. The I···Pd and I···E bonds are comparable in strength (the bond interaction energies being between -7 and -13 kcal/mol), but the former is controlled by dispersion forces, while the latter is mostly governed by an electrostatic term.

KW - NONCOVALENT INTERACTIONS

KW - QUANTITATIVE-ANALYSIS

KW - PERTURBATION-THEORY

KW - CRYSTAL-STRUCTURES

KW - SIGMA-HOLE

KW - COMPLEXES

KW - MOLECULES

KW - ENERGIES

KW - CHALCOGEN

KW - PROGRAM

UR - http://www.scopus.com/inward/record.url?scp=85100157190&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/ae0c99ba-da7f-33a7-8234-a826a7d0c322/

U2 - 10.1021/acs.cgd.0c01474

DO - 10.1021/acs.cgd.0c01474

M3 - Article

AN - SCOPUS:85100157190

VL - 21

SP - 1159

EP - 1177

JO - Crystal Growth and Design

JF - Crystal Growth and Design

SN - 1528-7483

IS - 2

ER -