A1 Journal article (refereed)
Halogen Bonding Involving Palladium(II) as an XB Acceptor (2021)

Katlenok, E. A., Rozhkov, A. V., Levin, O. V., Haukka, M., Kuznetsov, M. L., & Kukushkin, V. Y. (2021). Halogen Bonding Involving Palladium(II) as an XB Acceptor. Crystal Growth and Design, 21(2), 1159-1177. https://doi.org/10.1021/acs.cgd.0c01474

JYU authors or editors

Publication details

All authors or editors: Katlenok, Eugene A.; Rozhkov, Anton V.; Levin, Oleg V.; Haukka, Matti; Kuznetsov, Maxim L.; Kukushkin, Vadim Yu.

Journal or series: Crystal Growth and Design

ISSN: 1528-7483

eISSN: 1528-7505

Publication year: 2021

Publication date: 31/12/2020

Volume: 21

Issue number: 2

Pages range: 1159-1177

Publisher: American Chemical Society (ACS)

Publication country: United States

Publication language: English

DOI: https://doi.org/10.1021/acs.cgd.0c01474

Publication open access: Not open

Publication channel open access: 

Abstract

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.

Keywords: coordination complexes; palladium; chemical bonds

Free keywords: palladium; x-rays; ligands; noncovalent interactions; molecular interactions

Contributing organizations

Ministry reporting: Yes

Reporting Year: 2021

JUFO rating: 2