Design Platform for Sustainable Catalysis with Radicals: Electrochemical Activation of Cp2TiCl2 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 EqCr equilibrium of Cp2TiCl2. We have, for the first time, provided quantitative data for the EqCr equilibrium and have determined the stoichiometry of adduct formation of [Cp2Ti(III)Cl-2](-), [Cp2Ti(III)Cl] and [Cp2Ti(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 EqCr equilibrium as predictor for sustainable catalysis. They are also a design platform for the development of novel additives in particular for enantioselective catalysis.

Automated summary

The study successfully elucidated the impact of compounds such as thiourea, squaramide, and bissulfonamide on the EqCr equilibrium of Cp2TiCl2 through a combination of synthesis, electrochemical measurements, computational investigations, and DFT methods. Quantitative data and stoichiometry of adduct formation were provided for the first time, along with the determination of Gibbs energies, enthalpies, and complex structures. The results not only validated the use of the EqCr equilibrium in predicting sustainable catalysis, but also served as a design platform for the development of novel additives, particularly in enantioselective catalysis.