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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.

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 )4 AuL (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 R3 PAuX to give Au(III) perfluorinated auracycles. Evidence of a radical mechanism for these decomposition reactions was obtained.

SUBMITTER: Portugues A 

PROVIDER: S-EPMC9291513 | biostudies-literature | 2021 Nov

REPOSITORIES: biostudies-literature

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Dinuclear Au(I), Au(II) and Au(III) Complexes with (CF<sub>2</sub> )<sub>n</sub> Chains: Insights into The Role of Aurophilic Interactions in the Au(I) Oxidation.

Portugués Alejandro A   Bautista Delia D   Gil-Rubio Juan J  

Chemistry (Weinheim an der Bergstrasse, Germany) 20210929 63

New dinuclear Au(I), Au(II) and Au(III) complexes containing (CF<sub>2</sub> )<sub>n</sub> bridging chains were obtained. Metallomacrocycles [Au<sub>2</sub> {μ-(CF<sub>2</sub> )<sub>4</sub> }{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(CF<sub>2</sub> )<sub>4</sub> AuL (L=PPh<sub>3</sub> , PMe<sub>3</sub> , (dppf)<sub>1/2</sub> , (bin  ...[more]

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