title: Uncovering the Role of Oxygen Atom Transfer in Ru-Based Catalytic Water Oxidation.
abstract: The realization of artificial photosynthesis carries the promise of cheap and abundant energy, however, significant advances in the rational design of water oxidation catalysts are required. Detailed information on the structure of the catalyst under reaction conditions and mechanisms of O-O bond formation should be obtained. Here, we used a combination of electron paramagnetic resonance (EPR), stopped flow freeze quench on a millisecond-second time scale, X-ray absorption (XAS), resonance Raman (RR) spectroscopy, and density functional theory (DFT) to follow the dynamics of the Ru-based single site catalyst, [RuII(NPM)(4-pic)2(H2O)]2+(NPM = 4-t-butyl-2,6-di(1',8'-naphthyrid-2'-yl)pyridine, pic = 4-picoline), under the water oxidation conditions. We report a unique EPR signal with g-tensor, gx= 2.30, gy= 2.18, and gz= 1.83 which allowed us to observe fast dynamics of oxygen atom transfer from the RuIV═O oxo species to the uncoordinated nitrogen of the NPM ligand. In few seconds, the NPM ligand modification results in [RuIII(NPM-NO)(4-pic)2(H2O)]3+and [RuIII(NPM-NO,NO)(4-pic)2]3+complexes. A proposed [RuV(NPM)(4-pic)2═O]3+intermediate was not detected under the tested conditions. We demonstrate that while the proximal base might be beneficial in O-O bond formation via nucleophilic water attack on an oxo species as shown by DFT, the noncoordinating nitrogen is impractical as a base in water oxidation catalysts due to its facile conversion to the N-O group. This study opens new horizons for understanding the real structure of Ru catalysts under water oxidation conditions and points toward the need to further investigate the role of the N-O ligand in promoting water oxidation catalysis.
authors: Department of Physics and Astronomy, Purdue University , 525 Northwestern Avenue, West Lafayette, Indiana 47907, United States.|Chemical Sciences and Engineering Division, Argonne National Laboratory , 9700 S. Cass Avenue, Lemont, Illinois 60439, United States.
authors: Dooshaye
authors: D
authors: Moonshiram
authors: Department of Physics and Astronomy, Purdue University , 525 Northwestern Avenue, West Lafayette, Indiana 47907, United States.
authors: Yuliana
authors: Y
authors: Pineda-Galvan
authors: Department of Physics and Astronomy, Purdue University , 525 Northwestern Avenue, West Lafayette, Indiana 47907, United States.
authors: Darren
authors: D
authors: Erdman
authors: Code 6189, Chemistry Division, Naval Research Laboratory , 4555 Overlook Avenue SW, Washington, DC 20375, United States.
authors: Mark
authors: M
authors: Palenik
authors: Department of Chemistry, University of Houston , Houston, Texas 77204-5003, United States.
authors: Ruifa
authors: R
authors: Zong
authors: Department of Chemistry, University of Houston , Houston, Texas 77204-5003, United States.
authors: Randolph
authors: R
authors: Thummel
authors: Department of Physics and Astronomy, Purdue University , 525 Northwestern Avenue, West Lafayette, Indiana 47907, United States.
authors: Yulia
authors: Y
authors: Pushkar