TY - JOUR

T1 - Bifurcated Halogen Bonding Involving Diaryliodonium Cations as Iodine(III)-Based Double-σ-Hole Donors

AU - Aliyarova, Irina S.

AU - Ivanov, Daniil M.

AU - Soldatova, Natalia S.

AU - Novikov, Alexander S.

AU - Postnikov, Pavel S.

AU - Yusubov, Mekhman S.

AU - Kukushkin, Vadim Yu

N1 - Funding Information: This study integrates two separate projects supported by the Russian Foundation for Basic Research (project 20-33-90029; synthetic and X-ray diffraction experiments) and the Russian Science Foundation (project 20-13-00144; theoretical calculations). The authors are grateful to the Center for X-ray Diffraction Studies, Magnetic Resonance Research Center, and the Center for Chemical Analysis and Materials Research (all belonging to Saint Petersburg State University) for the physicochemical studies. V.Y.K. thanks South Ural State University (Act 211 Government of the Russian Federation, contract 02.A03.21.0011) for providing their facilities to the authors. Publisher Copyright: © Copyright: Copyright 2021 Elsevier B.V., All rights reserved.

PY - 2021/2/3

Y1 - 2021/2/3

N2 - Three diaryliodonium tetrachloroaurates(III), [Ar1IAr2][AuCl4] (Ar1/Ar2 = Ph/Ph (1), Ph/Mes (2), o-(C6H4)2 (3)), were obtained as solids (62-80%) by the metathetical reaction of [Ar1IAr2](CF3CO2) and H[AuCl4]. In particular, the single-crystal X-ray diffraction studies of 1-3 revealed three-center bifurcated C-I···(Cl-Au-Cl) halogen bond (XB) and the more conventional interionic two-center C-I···Cl-Au XB. An XB with the iodine(III) center of a diaryliodonium cation can be formed even when ∠(C-I···X) is much less than 180° (decrease by 55° in our experiments). A Cambridge Structural Database search and processing revealed other examples of bifurcated XBs involving diaryliodonium species. All recognized bifurcated XBs with diaryliodonium cations were classified and divided into two categories: "bifurcated plus two-center"and "double-bifurcated"structural types. The nature and energies of the XB interactions were studied by density functional theory (DFT) calculations and a topological analysis of the electron density distribution in the framework of the quantum theory of atoms in molecules (QTAIM) at the ωB97XD/DZP-DKH level of theory. The nature of all XB contacts is purely noncovalent, and the total energy of bifurcated XBs is generally ca. 50% higher than the energy of two-center XBs.

AB - Three diaryliodonium tetrachloroaurates(III), [Ar1IAr2][AuCl4] (Ar1/Ar2 = Ph/Ph (1), Ph/Mes (2), o-(C6H4)2 (3)), were obtained as solids (62-80%) by the metathetical reaction of [Ar1IAr2](CF3CO2) and H[AuCl4]. In particular, the single-crystal X-ray diffraction studies of 1-3 revealed three-center bifurcated C-I···(Cl-Au-Cl) halogen bond (XB) and the more conventional interionic two-center C-I···Cl-Au XB. An XB with the iodine(III) center of a diaryliodonium cation can be formed even when ∠(C-I···X) is much less than 180° (decrease by 55° in our experiments). A Cambridge Structural Database search and processing revealed other examples of bifurcated XBs involving diaryliodonium species. All recognized bifurcated XBs with diaryliodonium cations were classified and divided into two categories: "bifurcated plus two-center"and "double-bifurcated"structural types. The nature and energies of the XB interactions were studied by density functional theory (DFT) calculations and a topological analysis of the electron density distribution in the framework of the quantum theory of atoms in molecules (QTAIM) at the ωB97XD/DZP-DKH level of theory. The nature of all XB contacts is purely noncovalent, and the total energy of bifurcated XBs is generally ca. 50% higher than the energy of two-center XBs.

KW - CRYSTAL-STRUCTURE

KW - VIBRATIONAL-SPECTRA

KW - HYPERVALENT IODINE

KW - COMPLEX HALIDES

KW - NONCOVALENT INTERACTIONS

KW - IODONIUM SALTS

KW - WEAK

KW - DERIVATIVES

KW - REAGENTS

KW - HYBRIDS

UR - http://www.scopus.com/inward/record.url?scp=85100261257&partnerID=8YFLogxK

U2 - 10.1021/acs.cgd.0c01463

DO - 10.1021/acs.cgd.0c01463

M3 - Article

AN - SCOPUS:85100261257

VL - 21

SP - 1136

EP - 1147

JO - Crystal Growth and Design

JF - Crystal Growth and Design

SN - 1528-7483

IS - 2

ER -