Catalytic N–H Bond Formation Promoted by a Ruthenium Hydride Complex Bearing a Redox-Active Pyrimidine-Imine Ligand
The synthesis of a piano-stool ruthenium hydride, [(η 5 -C 5 Me 5 )Ru(PmIm)H] (PmIm = (N-(1,3,5-trimethylphenyl)-1-(pyrimidin-2-yl)ethan-1-imine) for the dual purpose of catalytic dihydrogen activation and subsequent hydrogen atom transfer for the formation of weak chemical bonds is described. Introduction of a neutral, potentially redox-active PmIm supporting ligand was designed to eliminate the possibility of deleterious C(sp 2 )–H reductive coupling and elimination that has been identified as a deactivation pathway with related rhodium and iridium catalysts. Treatment of [(η 5 -C 5 Me 5 )RuCl 2 ] n with one equivalent PmIm ligand in the presence of zinc and sodium methoxide resulted in isolation of the diruthenium complex, [(η 5 -C 5 Me 5 )Ru(PmIm)] 2 , arising from C–C bond formation between two PmIm chelates. Addition of H 2 to the ruthenium dimer under both thermal and blue light irradiation conditions furnished the targeted hydride, [(η 5 -C 5 Me 5 )Ru(PmIm)H] which has a relatively weak DFT-calculated Ru–H bond dissociation free energy (BDFE) of 47.9 kcal/mol. Addition of TEMPO to [(η 5 -C 5 Me 5 )Ru(PmIm)H] generated the 17-electron metalloradical, [(η 5 -C 5 Me 5 )Ru(PmIm)], which was characterized by EPR spectroscopy. The C–C bond forming process was reversible as irradiation of [(η 5 -C 5 Me 5 )Ru(PmIm)] 2 generated [(η 5 -C 5 Me 5 )Ru(PmIm)H] and a piano-stool ruthenium complex containing an enamide ligand derived from H-atom ab-straction from the PmIm chelate. Equilibration studies were used to establish an experimental estimate of the effective Ru–H BDFE and a value of 50.8 kcal/mol was obtained, in agreement with the observed loss of H 2 and the DFT-computed value. Here, the ruthenium hydride was an effective catalyst for the thermal catalytic hydrogenation of TEMPO, acridine and a cobalt-imido complex and for the selective reduction of azobenzene to diphenylhydrazine using H 2 as the terminal reductant, highlighting the role of this complex is catalytic weak bond formation using H 2 as the stoichiometric reductant.