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

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

doi:10.1021/jacs.2c07800

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

Journal Article · Thu Nov 03 00:00:00 EDT 2022 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.2c07800· OSTI ID:1900030

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Princeton Univ., NJ (United States); Princeton University
Princeton Univ., NJ (United States)

The synthesis of a piano-stool ruthenium hydride, [(η⁵-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. 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 [(η⁵-C₅Me₅)RuCl₂]_n with one equivalent PmIm ligand in the presence of zinc and sodium methoxide resulted in isolation of the diruthenium complex, [(η⁵-C₅Me₅)Ru(PmIm)]₂, arising from C–C bond formation between two PmIm chelates. Addition of H₂ to the ruthenium dimer under both thermal and blue light irradiation conditions furnished the targeted hydride, [(η⁵-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 [(η⁵-C₅Me₅)Ru(PmIm)H] generated the 17-electron metalloradical, [(η⁵-C₅Me₅)Ru(PmIm)], which was characterized by EPR spectroscopy. The C–C bond forming process was reversible as irradiation of [(η⁵-C₅Me₅)Ru(PmIm)]₂ generated [(η⁵-C₅Me₅)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 H₂ 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 H₂ as the terminal reductant, highlighting the role of this complex is catalytic weak bond formation using H₂ as the stoichiometric reductant.

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Research Organization:: Princeton Univ., NJ (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0006498

OSTI ID:: 1900030

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 45 Vol. 144; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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