Design Platform for Sustainable Catalysis with Radicals: Electrochemical Activation of Cp2 TiCl2 for Catalysis Unveiled.

The combination of synthesis, rotating ring-disk electrode (RRDE) and cyclic voltammetry (CV) measurements, and computational investigations with the aid of DFT methods shows how a thiourea, a squaramide, and a bissulfonamide as additives affect the Eq Cr equilibrium of Cp2 TiCl2 . We have, for the first time, provided quantitative data for the Eq Cr equilibrium and have determined the stoichiometry of adduct formation of [Cp2 Ti(III)Cl2 ]- , [Cp2 Ti(III)Cl] and [Cp2 Ti(IV)Cl2 ] and the additives. By studying the structures of the complexes formed by DFT methods, we have established the Gibbs energies and enthalpies of complex formation as well as the adduct structures. The results not only demonstrate the correctness of our use of the Eq Cr equilibrium as predictor for sustainable catalysis. They are also a design platform for the development of novel additives in particular for enantioselective catalysis.