TY - JOUR

T1 - Halogen bonding involving gold nucleophiles in different oxidation states

AU - Алиярова, Ирина Сергеевна

AU - Тупикина, Елена Юрьевна

AU - Солдатова, Наталья Сергеевна

AU - Иванов, Даниил Михайлович

AU - Постников, Павел

AU - Юсубов, М.С.

AU - Кукушкин, Вадим Юрьевич

N1 - Publisher Copyright: © 2022 American Chemical Society. All rights reserved.

PY - 2022/10/3

Y1 - 2022/10/3

N2 - A single-crystal X-ray diffraction (XRD) study of diaryliodonium tetrachloroaurates (or, in the recent terminology, tetrachloridoaurates), [(p-XC 6H 4) 2I][AuCl 4] (X = Cl, 1; Br, 2), was performed for 1 (the structure is denoted as 1a to show similarity with the isomorphic structure 2a) and two polymorphs-2a (obtained from MeOH) and 2b (from 1,2-C 2H 4Cl 2). Examination of the XRD data for these three structures revealed 2-center C-X···Au III(X = Cl and Br) and 3-center bifurcated C-Br···(Cl-Au) halogen bonding (abbreviated as XB) between the p-Cl or p-Br atoms of the diaryliodonium cations and the gold(III) atom of [AuCl 4] -. The noncovalent nature of Au III-involving interactions, the nucleophilicity of the gold(III) atoms, and the electrophilic role of p-X atoms of the diaryliodonium cations in the XBs were studied by a set of complementary computational methods. Combined experimental and theoretical studies allowed the recognition of the d-nucleophilicity of the [d 8Au III] atom which, regardless of its rather substantial formal 3+ charge, can function as a d-nucleophilic partner of XB. This conclusion was also supported by theoretical calculations performed for the structures' refcodes BINXOM and ICSD 62511; the obtained data verified the nucleophilicity of Au IIItoward a K +ions or a σ-(Cl)-hole, respectively. All our results, together with consideration of relevant literature, indicate that gold atoms in the three oxidation states (0, I, and even III) exhibit nucleophilicity in XBs.

AB - A single-crystal X-ray diffraction (XRD) study of diaryliodonium tetrachloroaurates (or, in the recent terminology, tetrachloridoaurates), [(p-XC 6H 4) 2I][AuCl 4] (X = Cl, 1; Br, 2), was performed for 1 (the structure is denoted as 1a to show similarity with the isomorphic structure 2a) and two polymorphs-2a (obtained from MeOH) and 2b (from 1,2-C 2H 4Cl 2). Examination of the XRD data for these three structures revealed 2-center C-X···Au III(X = Cl and Br) and 3-center bifurcated C-Br···(Cl-Au) halogen bonding (abbreviated as XB) between the p-Cl or p-Br atoms of the diaryliodonium cations and the gold(III) atom of [AuCl 4] -. The noncovalent nature of Au III-involving interactions, the nucleophilicity of the gold(III) atoms, and the electrophilic role of p-X atoms of the diaryliodonium cations in the XBs were studied by a set of complementary computational methods. Combined experimental and theoretical studies allowed the recognition of the d-nucleophilicity of the [d 8Au III] atom which, regardless of its rather substantial formal 3+ charge, can function as a d-nucleophilic partner of XB. This conclusion was also supported by theoretical calculations performed for the structures' refcodes BINXOM and ICSD 62511; the obtained data verified the nucleophilicity of Au IIItoward a K +ions or a σ-(Cl)-hole, respectively. All our results, together with consideration of relevant literature, indicate that gold atoms in the three oxidation states (0, I, and even III) exhibit nucleophilicity in XBs.

UR - http://www.scopus.com/inward/record.url?scp=85138981861&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/ad3c8924-8bf0-3b38-aa1a-5d9bab46b246/

U2 - 10.1021/acs.inorgchem.2c01858

DO - 10.1021/acs.inorgchem.2c01858

M3 - Article

VL - 61

SP - 15398

EP - 15407

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 39

ER -