Au(iii)-aryl intermediates in oxidant-free C-N and C-O cross-coupling catalysis.

Au(iii)-aryl species have been unequivocally identified as reactive intermediates in oxidant-free C-O and C-N cross coupling catalysis. The crystal structures of cyclometalated neutral and cationic Au(iii) species are described and their key role in 2 electron-redox Au(i)/Au(iii) catalysis in C-O and C-N cross couplings is shown. Nucleophiles compatible with Au-catalyzed cross couplings include aromatic and aliphatic alcohols and amines, as well as water and amides.