Mechanistic studies on pincer-complex reactivities with photo-chemical methodes

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The aim of the proposed research project is to do an extensive study on labile reaction intermediates of pincer-complexes, important to CH-activation and (de)hydrogenation reactions, as well as the collection of kinetic data concerning substitution reactions at these complexes. These substances and processes, which are of immense importance for the understanding of pincer-complexes and their reactivity, are hard to detect by classical approaches but may easily be characterised via their photochemistry. Therefore this investigation is based on NMR spectroscopy with in situ irradiation in the probe, on the unique NMR photochemistry setup at the University of York, classical laser flash photolysis experiments and preparative photochemical techniques. During the 18 months anticipated for the postdoctoral research project, the investigations will broaden the mechanistic understanding of the important class of pincer-type transition metal complexes by an extensive photochemical study. The dissociative photochemistry should give insight into the properties of labile reaction intermediates important to CH-activation and (de)hydrogenation reactions as well as the general kinetics of substitution reactions on pincer complexes. With the proposed preparative photochemical experiments a classification of electronic and steric properties of typical substrates for pincer-complex catalysed reactions should be possible. This could become a crucial step forward for the directed optimisation of these catalysts.