Dispersion Interaction in Metal- and Organocatalysis - Assessment and Implementation in Salalen Ligands and N-Heterocyclic Carbenes

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Understand - quantify - use: Our studies aim at the assessment and implementation of dispersion control in two areas of small-molecule homogeneous catalysis: (i) titanium-salalen complexes for the asymmetric epoxidation of non-functionalized and in particular terminal olefins with hydrogen peroxide, and (ii) N-heterocyclic carbenes for Umpolung reactions in organocatalysis and as ligands in metal-catalyzed C-H activation. By the introduction of dispersion energy donors (DEDs) into the two catalyst systems, significant experimental progress and mechanistic insight was achieved in both areas in the course of the first funding period. For the second funding period, we are intending to build on this body of information, and to provide, by rational approach, novel, readily available and broadly applicable catalyst generations. Mechanistic studies will aim at a thorough understanding of their modes of action, and in particular of the role of dispersion. This multi-level approach is intended to contribute, on one hand, to our understanding of dispersion control of molecular catalytic transformations. On the other hand, by rational incorporation of dispersion elements, we are aiming at novel catalyst generations of unprecedented activity and selectivity. The project will combine, in a synergistic manner, synthesis, spectroscopy, mechanistic analyses, and quantum-chemical computation. Several cooperations with other research groups are integral part of this endeavor.