Ruthenium PNN(O) Complexes: Cooperative Reactivity and Application as Catalysts for Acceptorless Dehydrogenative Coupling Reactions.

The novel tridentate PNN pincer ligand features a reactive 2-hydroxypyridine functionality as well as a bipyridyl-methylphosphine skeleton for meridional coordination. This proton-responsive ligand coordinates in a straightforward manner to RuCl(CO)(H)(PPh) to generate complex . The methoxy-protected analogue was also coordinated to Ru(II) for comparison. Both species have been crystallographically characterized. Site-selective deprotonation of the 2-hydroxypyridine functionality to give was achieved using both mild (DBU) and strong bases (KOBu and KHMDS), with no sign of involvement of the phosphinomethyl side arm that was previously established as the reactive fragment. Complex is catalytically active in the dehydrogenation of formic acid to generate CO-free hydrogen in three consecutive runs as well as for the dehydrogenative coupling of alcohols, giving high conversions to different esters and outperforming structurally related PNN ligands lacking the N fragment. DFT calculations suggest more favorable release of H through reversible reactivity of the hydroxypyridine functionality relative to the phosphinomethyl side arm.