Catalytic N-H Bond Formation Promoted by a Ruthenium Hydride Complex Bearing a Redox-Active Pyrimidine-Imine Ligand

Sangmin Kim, Junho Kim, Hongyu Zhong, Grace B. Panetti, Paul J. Chirik

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Abstract

The synthesis of a piano-stool ruthenium hydride, [(Ε5-C5Me5)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. The introduction of a neutral, potentially redox-active PmIm supporting ligand was designed to eliminate the possibility of deleterious C(sp2)-H reductive coupling and elimination that has been identified as a deactivation pathway with related rhodium and iridium catalysts. Treatment of [(Ε5-C5Me5)RuCl2]nwith one equivalent PmIm ligand in the presence of zinc and sodium methoxide resulted in the isolation of the diruthenium complex, [(Ε5-C5Me5)Ru(PmIm)]2, arising from the C-C bond formation between two PmIm chelates. Addition of H2to the ruthenium dimer under both thermal and blue light irradiation conditions furnished the targeted hydride, [(Ε5-C5Me5)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 [(Ε5-C5Me5)Ru(PmIm)H] generated the 17-electron metalloradical, [(Ε5-C5Me5)Ru(PmIm)], which was characterized by EPR spectroscopy. The C-C bond forming process was reversible as the irradiation of [(Ε5-C5Me5)Ru(PmIm)]2generated [(Ε5-C5Me5)Ru(PmIm)H] and a piano-stool ruthenium complex containing an enamide ligand derived from H-atom abstraction 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 H2and the DFT-computed value. 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, highlighting the role of this complex in catalytic weak bond formation using H2as the stoichiometric reductant.

Original languageEnglish (US)
Pages (from-to)20661-20671
Number of pages11
JournalJournal of the American Chemical Society
Volume144
Issue number45
DOIs
StatePublished - Nov 16 2022

All Science Journal Classification (ASJC) codes

  • General Chemistry
  • Biochemistry
  • Catalysis
  • Colloid and Surface Chemistry

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