Design Platform for Sustainable Catalysis with Radicals: Electrochemical Activation of Cp(2)TiCl(2) 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 E(q)C(r) equilibrium of Cp(2)TiCl(2). We have, for the first time, provided quantitative data for the E(q)C(r) equilibrium and have determined the stoichiometry of adduct formation of [Cp(2)Ti(III)Cl(2)](−), [Cp(2)Ti(III)Cl] and [Cp(2)Ti(IV)Cl(2)] 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 E(q)C(r) equilibrium as predictor for sustainable catalysis. They are also a design platform for the development of novel additives in particular for enantioselective catalysis.