Recently, the discovery of a 2-hydroxypyridine-derived cofactor in the active site of the hydrogenase metalloenzyme [Fe]-hmd renewed interest in multifunctional systems that incorporate 2-hydroxypyridine (2-hp) motifs to mediate substrate activation in synthetic hydrogenation catalysts. Our research group is targeting metal-ligand constructs that contain appended functionality, capable of cooperative substrate activation. This presentation will outline efforts that target the incorporation of 2-hp units within rigid ligand systems for rapid hydrogen-transfer reactivity. The ability of the associated ruthenium complexes to engage a substrate in both primary and secondary coordination-sphere interactions will be discussed. Furthermore, H2 activation pathways of the ruthenium(II) complexes will be outlined as they pertain to chemoselective-hydrogenation catalysis. Particular emphasis will be placed on synthetic approaches and design strategies to generate rigid ligand systems that feature a very low kinetic barrier for H2 activation, as well as mechanistic efforts that target key intermediates involved in cooperative heterolytic splitting of H2.

Terpyridine-derived ligands for metal-ligand cooperativity in ruthenium hydrogenation catalysis

245th National Meeting (2013)

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