Halogen Bonding Involving Gold Nucleophiles in Different Oxidation States
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22310%2F22%3A43925998" target="_blank" >RIV/60461373:22310/22:43925998 - isvavai.cz</a>
Result on the web
<a href="https://pubs.acs.org/doi/10.1021/acs.inorgchem.2c01858" target="_blank" >https://pubs.acs.org/doi/10.1021/acs.inorgchem.2c01858</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/acs.inorgchem.2c01858" target="_blank" >10.1021/acs.inorgchem.2c01858</a>
Alternative languages
Result language
angličtina
Original language name
Halogen Bonding Involving Gold Nucleophiles in Different Oxidation States
Original language description
A single-crystal X-ray diffraction (XRD) study of diaryliodonium tetrachloroaurates (or, in the recent terminology, tetrachloridoaurates), [(p-XC6H4)2I][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···AuIII(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 [AuCl4]-. The noncovalent nature of AuIII-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 [d8AuIII] 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 AuIIItoward 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. © 2022 American Chemical Society. All rights reserved.
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
20501 - Materials engineering
Result continuities
Project
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Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2022
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Inorganic Chemistry
ISSN
0020-1669
e-ISSN
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Volume of the periodical
61
Issue of the periodical within the volume
39
Country of publishing house
US - UNITED STATES
Number of pages
10
Pages from-to
15398-15407
UT code for WoS article
000861612900001
EID of the result in the Scopus database
2-s2.0-85138981861