Aerobic benzyl alcohol oxidation by copper(I)(2,2′-bipyridine)-based catalysts

[Display omitted] •Cu(I)-2,2′-bipyridine pre-catalysts for the aerobic benzyl alcohol oxidation.•Catalytic activity steered by ligand counter-anion interaction in acetonitrile.•Benzaldehyde selectivity depends on the initial benzyl alcohol concentration.•Ligand de-coordination found as the main deactivation path for the catalyst. “In situ” prepared cationic Cu(I) complexes bearing 2,2’-bipyridine ligands and trifluoromethylsulfonate (triflate) have been used to catalyze the aerobic oxidation of benzyl alcohol to benzaldehyde in acetonitrile in the presence of (2,2,6,6-tetramethylpiperidin-1-yl) oxyl (TEMPO). A combination of catalytic reactions, operando1H NMR spectroscopic studies and the analysis of the molecular structure of the Cu(I) precatalysts in acetonitrile by means of DFT calculations shed light on the notable influence of counter-anion ligand interactions on the observed catalytic activity.