Transition Metal Complexes with Chiral Pincer Ligands: Reactions, Catalyses, Mechanisms

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The research project concerns the coordination chemistry of such chiral pincer ligands as stereodirecting ligands in enantioselective catalysis. A main objective will be to assess to which extent this class of ligands may serve als "privileged" stereodirecting ligand systems in a diverse range of enantioselective transformations. An aim of the planned research will be the isolation and characterization of (high spin) hydrido and boranato-derivatives of Boxmi-manganese, iron, cobalt and nickel complexes as key intermediates of enantioselective catalytic reductions with these 3d metals as well as the use of the isolated complexes in systematic kinetic studies of the stoichiometric and catalytic reductions. Furthermore, we aim to develop efficient oxidation catalysts based on the recently discovered Ni(I/II) catalyzed radikal oxygenations with O2 as co-substrate, and ongoing mechanistic studies of these transformations will be continued and pursued to greater depth. Finally we plan to investigate Boxmi-manganese complexes as possible catalysts for the enantioselective alpha-acyloxylation of ketones, the reaction mechanism(s) and identify the (electronically open shell, paramagnetic) complexes involved.