Enantio- and Diastereomerically Pure Titanocenes by Dynamic Conformational Locking.

The synthesis of enantiomerically pure titanocenes is limited to cases with enantiomerically pure substituents at the cyclopentadienyl ligands and to ansa-titanocenes. For the latter complexes, the use of achiral ligands requires a resolution of enantiomers and frequently also a separation of the diastereoisomers obtained after metalation. Here, we introduce a new synthetic method that relies on the use of enantiomerically pure camphorsulfonate (CSA) ligands as control elements for the absolute and relative configuration of titanocene complexes. Starting from the conformationally flexible (RC5 H4 )2 TiCl2 , the desired conformationally locked and hence enantio- and diastereomerically pure complexes (RC5 H4 )2 Ti(CSA)2 are obtained in just two steps. According to X-ray crystallography the (RC5 H4 )2 Ti fragment is essentially C2 -symmetric and nuclear magnetic resonance displays overall C2 -symmetry. We applied density functional theory methods to unravel the dynamics of the complexes and the mechanisms and selectivities of their formation.

Design Platform for Sustainable Catalysis with Radicals: Electrochemical Activation of Cp2 TiCl2 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 Eq Cr equilibrium of Cp2 TiCl2 . We have, for the first time, provided quantitative data for the Eq Cr equilibrium and have determined the stoichiometry of adduct formation of [Cp2 Ti(III)Cl2 ]- , [Cp2 Ti(III)Cl] and [Cp2 Ti(IV)Cl2 ] 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 Eq Cr equilibrium as predictor for sustainable catalysis. They are also a design platform for the development of novel additives in particular for enantioselective catalysis.

Titanocenes as Photoredox Catalysts Using Green-Light Irradiation.

Irradiation of Cp2 TiCl2 with green light leads to electronically excited [Cp2 TiCl2 ]*. This complex constitutes an efficient photoredox catalyst for the reduction of epoxides and for 5-exo cyclizations of suitably unsaturated epoxides. To the best of our knowledge, our system is the first example of a molecular titanium photoredox catalyst.

Condition Screening for Sustainable Catalysis in Single-Electron Steps by Cyclic Voltammetry: Additives and Solvents.

Cyclic voltammetry-based screening method for Cp2 TiX-catalyzed reactions is extended to the screening of solvents other than tetrahydrofuran for bulk electrolysis of the catalyst and radical arylation. It was found that CH3 CN can be used as a solvent for both processes without additives. Furthermore, in tetrahydrofuran, squaramide L2 is more efficient than the previously reported supramolecular halide binder, Schreiner's thiourea L1. The results extend the usefulness of the proposed time and resource-efficient screening method for designing catalysis reactions in single-electron steps.