Ligand-enabled oxidation of gold(i) complexes with o-quinones

György Szalóki (1) , Julien Babinot (1) , Vlad Martin-Diaconescu (2) , Sonia Mallet-Ladeira (3) , Yago García-Rodeja (4) , Karinne Miqueu (4) , Didier Bourissou (1)

1 LHFA - Laboratoire Hétérochimie Fondamentale et Appliquée
2 CELLS ALBA - CELLS ALBA synchroton = ALBA Synchrotron
3 ICT - Institut de Chimie de Toulouse
4 IPREM - Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux

Chelating P^P and hemilabile P^N ligands were found to trigger the oxidation of Au(I) complexes by obenzoquinones. The ensuing Au(III) catecholate complexes have been characterized by NMR spectroscopy, single crystal X-ray diffraction and X-ray absorption spectroscopy. They adopt tetracoordinate square-planar structures. Reactivity studies substantiate the reversibility of the transformation. In particular, the addition of competing ligands such as chloride and alkenes gives back Au(I) complexes with concomitant release of the o-quinone. DFT calculations provide insight about the structure and relative stability of the Au(I) o-quinone and Au(III) catecholate forms, and shed light on the 2-electron transfer from gold to the o-quinone.

Domaines: Chimie; Chimie analytique; Chimie théorique et/ou physique

György Szalóki, Julien Babinot, Vlad Martin-Diaconescu, Sonia Mallet-Ladeira, Yago García-Rodeja, et al.. Ligand-enabled oxidation of gold(i) complexes with o-quinones. Chemical Science, 2022, 13, pp.10499 - 10505. ⟨10.1039/d2sc03724f⟩. ⟨hal-03842055⟩