Cp<sub>2</sub>TiX has become a valuable tool in sustainable organic synthesis. Examples include the arylations of epoxides and the syntheses of polycyclic tetrahydrofurans. The outcome of these atom-economical reactions critically depends on the redox properties of the titanocene catalyst. Its properties can be adjusted either by substituents at the cyclopentadienyl ring or by variation of the anion X. Here we show how the latter approach can accelerate the rate determining steps in the two reactions mentioned above. CV studies determine the effect of different anions on the equilibrium of the four possible titanocene(III) species in solution and on their electrochemical potentials. Kinetical experiments provide further information about the different species. Weakly coordinating anions enhance the sustainability of the reactions by stabilizing reactive titanocenes further.

Effects of the anion X in Cp<sub>2</sub>TiX-catalyzed reactions

253rd National Meeting (2017)

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Effects of the anion X in Cp2TiX-catalyzed reactions

Effects of the anion X in Cp₂TiX-catalyzed reactions