Cp2TiX Complexes for Sustainable Catalysis in Single‐Electron Steps

We present a combined electrochemical, kinetic, and synthetic study with a novel and easily accessible class of titanocene catalysts for catalysis in single‐electron steps. The tailoring of the electronic properties of our Cp2TiX‐catalysts that are prepared in situ from readily available Cp2TiX2 is achieved by varying the anionic ligand X. Of the complexes investigated, Cp2TiOMs proved to be either equal or substantially superior to the best catalysts developed earlier. The kinetic and thermodynamic properties pertinent to catalysis have been determined. They allow a mechanistic understanding of the subtle interplay of properties required for an efficient oxidative addition and reduction. Therefore, our study highlights that efficient catalysts do not require the elaborate covalent modification of the cyclopentadienyl ligands. Modifications not necessary! With the aid of cyclic voltammetry and kinetic investigations Cp2TiX2 complexes with sulfonate ligands were identified as attractive catalysts in radical arylations and tetrahydrofuran synthesis. They do not require additives for catalyst stabilization and render the covalent modification of the cyclopentadienyl ligands superfluous for the tailoring of their performance in catalysis in single‐electron steps.