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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.
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Liedtke et al. (2018) studied this question.
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