Publication: Dinuclear Au(I), Au(II) and Au(III) Complexes with (CF2)n Chains: Insights into The Role of Aurophilic Interactions in the Au(I) Oxidation
Authors
Portugués, Alejandro ; Bautista, Delia ; Gil-Rubio, Juan
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Publisher
Wiley- VCH GmbH
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DOI
https://doi.org/10.1002/chem.202103153
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info:eu-repo/semantics/article
Description
© 2021.
Wiley. This document is made available under the CC-BY-NC 4.0 license http://creativecommons.org/licenses/by-nc /4.0/
This document is the accepted version of a published work that appeared in final form in
Chemistry - A European Journal.
Abstract
New dinuclear Au(I), Au(II) and Au(III) complexes containing (CF2)n bridging chains were obtained. Metallomacrocycles [Au2{μ-(CF2)4}{μ-diphosphine}] show an uncommon figure-eight structure, the helicity inversion barrier of which is influenced by aurophilic interactions and steric constraints imposed by the diphosphine. Halogenation of LAu(CF2)4AuL (L=PPh3, PMe3, (dppf)1/2, (binap)1/2) gave [Au(II)]2 species, some of which display unprecedented folded structures with Au –Au bonds. Aurophilic interactions facilitate this oxidation process by preorganizing the starting [Au(I)]2 complexes and lowering its redox potential. The obtained [Au(II)]2 complexes undergo thermal or photochemical elimination of R3PAuX to give Au(III) perfluorinated auracycles. Evidence of a radical mechanism for these decomposition reactions was obtained.
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Citation
Chemistry - A European Journal, 2021, vol. 27, issue 63, pag. 15815–15822
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