Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
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.
Язык оригинала | английский |
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Страницы (с-по) | 15398–15407 |
Число страниц | 10 |
Журнал | Inorganic Chemistry |
Том | 61 |
Номер выпуска | 39 |
DOI | |
Состояние | Опубликовано - 3 окт 2022 |
ID: 100022828