Between digold and nanoparticles : the selectivity of tetragold cationic catalyst
(in Chem. Eur. J. (2022))
For the first time, tetranuclear gold(I) dicationic complexes structurally supported by strongly stabilizing constraint diphosphinoferrocenyl ligands and attractive closed-shell Au∙∙∙Au aurophilic interactions illustrated a distinct and powerful selectivity for the activation of carbon-carbon multiple bonds in comparison to mononuclear gold Lewis-acid catalysts and digold complexes. More importantly this selectivity differs also from nanoparticles and heterogeneous gold catalysts reported to date. DFT studies correlated to experimental mechanistic investigations support an unprecedented “cluster-like” reactivity from polynuclear cooperation at the origin of this peculiar selectivity where the aurophilic interactions preexist, and pre-organize, gold cluster reactive intermediates.
Tetranuclear Dicationic Aurophilic Gold(I) Catalysts in Enyne Cycloisomerization: Cooperativity for a Dramatic Shift in Selectivity
Tuan-Anh Nguyen, Dr. E. Daiann Sosa Carrizo, Dr. Hélène Cattey, Prof. Dr. Paul Fleurat-Lessard, Dr. Julien Roger, Prof. Dr. Jean-Cyrille Hierso