4.7 Article

Halogen Bonding Involving Gold Nucleophiles in Different Oxidation States

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INORGANIC CHEMISTRY
卷 -, 期 -, 页码 -

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AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.2c01858

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  1. Russian Foundation for Basic Research [20-33-90029]
  2. Russian Science Foundation [20-13-00144]
  3. Ministry of Science and Higher Education of Russian Federation [075-15-2021-585]

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This study investigated the halogen bonding interactions in diaryliodonium tetrachloroaurates and found that gold(III) atoms exhibit nucleophilicity in these interactions, despite their substantial positive charge.
A single-crystal X-ray diffraction (XRD) study of diaryliodonium tetrachlor-oaurates (or, in the recent terminology, tetrachloridoaurates), [(p-XC6H4)(2)I][AuCl4] (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-C2H4Cl2). Examination of the XRD data for these three structures revealed 2-center C-X center dot center dot center dot Au-III (X = Cl and Br) and 3-center bifurcated C-Br center dot center dot center dot(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 [AuCl4](-). 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(8)Au(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-III toward a K+ ions or a sigma-(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.

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