Cooperative and Redox Non-innocent Ligands in Hydrogenation, Dehydrogenation and Dehydrogenative Coupling Reactions

This proposal aims at developing new catalytic approaches for challenging (new) reactions in homogeneous transition metal catalysis research. These investigations involve the use of redox non innocent and cooperative ligands to achieve challenging hydrogenation, dehydrogenation and dehydrogenative coupling reactions. The cooperative ligand is not just a spectator ligand, but actively participates in bond making and bond breaking processes in converting substrates to products. We will use recent insights in the chemical and redox non-innocence of picolyl-amido and related ligands to convert primary alcohols and amines to carboxylic acids, esters, amides, and imines. This will open new possibilities for selective chemical transformations, using new and selective catalysis based on cooperative substrate activation. The obtained insights in metal-ligand cooperative substrate activation using non-innocent and/or cooperative ligands may eventually allow us to increase the activity and reactivity of first row transition metal catalysts (in particular Fe and Co) in (de)hydrogenation reactions. As such, in a rational approach, we hope to contribute to the replacement of the currently applied 2nd and 3rd row transition metals by cheaper and less toxic first row transition metals.