Synthesis, Reactivity, and Catalytic Transfer Hydrogenation Activity of Ruthenium Complexes Bearing NNN Tridentate Ligands: Influence of the Secondary Coordination Sphere

[Image: see text] By the introduction of −OH group(s) into different position(s) of 6-(pyridin-2-ylmethyl)-2,2′-bipyridine, several NNN-type ligands were synthesized and then introduced to ruthenium (Ru) centers by reactions with RuCl(2)(PPh(3))(3). In the presence of PPh(3) or CO, these ruthenium complexes reacted with NH(4)PF(6) in CH(2)Cl(2) or CH(3)OH to give a series of ionic products 5–9. The reaction of Ru(L(2))(PPh(3))Cl(2) (2) with CO generated a neutral complex [Ru(L(2))(CO)Cl(2)] (10). In the presence of CH(3)ONa, 10 was further converted into complex [Ru(L(2))(HOCH(3))(CO)Cl] (11), in which there was a methanol molecule coordinating with ruthenium, as suggested by density functional theory calculations. The catalytic transfer hydrogenation activity of all of these new bifunctional metal–ligand complexes was tested. Dichloride complex 2 exhibits best activity, whereas carbonyl complexes 10 and 11 are efficient for selectively reducing 5-hexen-2-one, suggesting different hydrogenation mechanisms. The results reveal the dramatic influence for the reactivity and catalytic activity of the secondary coordination sphere in transition metal complexes.