Abstract

A new concept for the construction of bidentate ligands for homogeneous metal complex catalysis is described. The concept relies on the self-assembly of monodentate ligands through hydrogen bonding. As a prototype of such systems, 6-diphenylphosphanyl-2-pyridone (6-DPPon) was shown to form a chelate in the coordination sphere of a transition metal center through unusual pyridone/hydroxypyridine hydrogen bonding (X-ray). This hydrogen bonding stays intact in a catalytic reaction as proven upon highly regioselective hydroformylation of terminal alkenes. Regioselectivities and reactivities observed rank the 6-DPPon/rhodium system among the most active and regioselective catalysts for n-selective hydroformylation of terminal alkenes.

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