The Milstein Bipyridyl PNN Pincer Complex of Ruthenium Becomes a Noyori-Type Catalyst under Reducing Conditions.

Hydrogenation of the dearomatized PNN ligand of the Milstein bipyridyl complex RuH(CO)[PNN] (2) gives a square-pyramidal Ru(II) product RuH(CO)[pPNN] (5). The central ring of the pPNN ligand is a piperidine. A minor byproduct of the hydrogenation reaction is complex 6 which has a dimeric structure made of two Ru(II) fragments each possessing a partly hydrogenated PNN ligand. The structures of 5 and 6 have been elucidated by NMR spectroscopy and X-ray crystallography. The PNN ligand of 2 is also hydrogenated under the conditions of the catalytic dehydrogenative coupling of ethanol to ethyl acetate. No direct evidence of the aromatized dihydride RuH2(CO)[PNN] (4) was found in this study. However, treating RuHCl(CO)[PNN] with Li[HBEt3] or reacting 2 with H2 at low temperature resulted in a structurally characterized hydride-bridged dimer (7) bearing intact aromatized bipyridyl ligands. M06-L/def2-QZVP DFT calculations provided insights into the thermodynamics of the stoichiometric reactions of this work and into the nature of the intermediates of the catalytic ester hydrogenation facilitated by RuH2(CO)[pPN(H)N] (8) formed from 5 under H2.