Base-enhanced catalytic water oxidation by a carboxylate–bipyridine Ru(II) complex [electronic resource].
- Washington, D.C. : United States. Dept. of Energy. Office of Basic Energy Sciences, 2015.
Oak Ridge, Tenn. : Distributed by the Office of Scientific and Technical Information, U.S. Dept. of Energy
- Physical Description:
- pages 4,935-4,940 : digital, PDF file
- Additional Creators:
- United States. Department of Energy. Office of Basic Energy. Energy Frontier Research Centers (EFRC)
United States. Department of Energy. Office of Basic Energy Sciences
United States. Department of Energy. Office of Scientific and Technical Information
- In aqueous solution above pH 2.4 with 4% (vol/vol) CH<sub>3</sub>CN, the complex [Ru<sup>II</sup>(bda)(isoq)<sub>2</sub>] (bda is 2,2'-bipyridine-6,6'-dicarboxylate; isoq is isoquinoline) exists as the open-arm chelate, [Ru<sup>II</sup>(CO<sub>2</sub>-bpy-CO<sub>2</sub><sup>$-$</sup>)(isoq)<sub>2</sub>(NCCH<sub>3</sub>)], as shown by <sup>1</sup>H and <sup>13</sup>C-NMR, X-ray crystallography, and pH titrations. Rates of water oxidation with the open-arm chelate are remarkably enhanced by added proton acceptor bases, as measured by cyclic voltammetry (CV). In 1.0 M PO<sub>4</sub><sup>3–</sup>, the calculated half-time for water oxidation is ~7 μs. In conclusion, the key to the rate accelerations with added bases is direct involvement of the buffer base in either atom–proton transfer (APT) or concerted electron–proton transfer (EPT) pathways.
- Published through SciTech Connect.
Proceedings of the National Academy of Sciences of the United States of America 112 16 ISSN 0027-8424 AM
Na Song; Javier J. Concepcion; Robert A. Binstead; Jennifer A. Rudd; Aaron K. Vannucci; Christopher J. Dares; Michael K. Coggins; Thomas J. Meyer.
- Funding Information:
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