Mechanism-Based Condition Screening for Sustainable Catalysis in Single-Electron Steps by Cyclic Voltammetry.

A cyclic-voltammetry-based screening method for Cp2 TiX-catalyzed reactions is introduced. Our mechanism-based approach enables the study of the influence of various additives on the electrochemically generated active catalyst Cp2 TiX, which is in equilibrium with catalytically inactive [Cp2 TiX2 ]- . Thioureas and ureas are most efficient in the generation of Cp2 TiX in THF. Knowing the precise position of the equilibrium between Cp2 TiX and [Cp2 TiX2 ]- allowed us to identify reaction conditions for the bulk electrolysis of Cp2 TiX2 complexes and for Cp2 TiX-catayzed radical arylations without having to carry out the reactions. Our time- and resource-efficient approach is of general interest for the design of catalytic reactions that proceed in single-electron steps.