A coordinatively unsaturated iridium complex with an unsymmetrical redox-active ligand: (spectro)electrochemical and reactivity studies

. The same activation reaction was also tested for other haloforms. In all types of reactions, the masked coordination site at the metal center and the electron reservoir behavior of the redox-active ligand are used for reactivity. Furthermore, we show that the aforementioned iridium(iii) complex performs redox-induced dihydrogen activation. This activation process was used to catalytically transfer the electrons and protons of dihydrogen to a substrate molecule. Crystallographic, spectroscopic, electrochemical, spectroelectrochemical and DFT methods were used to elucidate the geometric and the electronic structures of the metal complex in the various redox forms and to probe the mechanism of the investigated reactions. We demonstrate here how the cooperative behavior between a catalytically active metal center and a redox non-innocent ligand can be utilized to perform substrate bond activation and transformation.