{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,6,10]],"date-time":"2026-06-10T14:27:44Z","timestamp":1781101664545,"version":"3.54.1"},"reference-count":41,"publisher":"National Academy of Sciences","issue":"52","content-domain":{"domain":["www.pnas.org"],"crossmark-restriction":true},"short-container-title":["Proc. Natl. Acad. Sci. U.S.A."],"published-print":{"date-parts":[[2011,12,27]]},"abstract":"\n In single site water or hydrocarbon oxidation catalysis with polypyridyl Ru complexes such as [Ru\n II<\/jats:sup>\n (Mebimpy)(bpy)(H\n 2<\/jats:sub>\n O)]\n 2+<\/jats:sup>\n [where bpy is 2,2\u2032-bipyridine, and Mebimpy is 2,6-bis(1-methylbenzimidazol-2-yl)pyridine]\n 2<\/jats:bold>\n , or its surface-bound analog [Ru\n II<\/jats:sup>\n (Mebimpy)(4,4\n \u2032<\/jats:sup>\n -bis-methlylenephosphonato-2,2\n \u2032<\/jats:sup>\n -bipyridine)(OH\n 2<\/jats:sub>\n )]\n 2+<\/jats:sup>\n 2<\/jats:bold>\n -\n PO<\/jats:bold>\n \n 3<\/jats:bold>\n <\/jats:sub>\n H<\/jats:bold>\n \n 2<\/jats:bold>\n <\/jats:sub>\n , accessing the reactive states, Ru\n V<\/jats:sup>\n \u00a0=\u00a0O\n 3+<\/jats:sup>\n \/Ru\n IV<\/jats:sup>\n \u00a0=\u00a0O\n 2+<\/jats:sup>\n , at the electrode interface is typically rate limiting. The higher oxidation states are accessible by proton-coupled electron transfer oxidation of aqua precursors, but access at inert electrodes is kinetically inhibited. The inhibition arises from stepwise mechanisms which impose high energy barriers for 1e\n -<\/jats:sup>\n intermediates. Oxidation of the Ru\n III<\/jats:sup>\n -OH\n 2+<\/jats:sup>\n or\n \n \n <\/jats:inline-formula>\n forms of\n 2<\/jats:bold>\n -\n PO<\/jats:bold>\n \n 3<\/jats:bold>\n <\/jats:sub>\n H<\/jats:bold>\n \n 2<\/jats:bold>\n <\/jats:sub>\n to Ru\n IV<\/jats:sup>\n \u00a0=\u00a0O\n 2+<\/jats:sup>\n on planar fluoride-doped SnO\n 2<\/jats:sub>\n electrode and in nanostructured films of Sn(IV)-doped In\n 2<\/jats:sub>\n O\n 3<\/jats:sub>\n and TiO\n 2<\/jats:sub>\n has been investigated with a focus on identifying microscopic phenomena. The results provide direct evidence for important roles for the nature of the electrode, temperature, surface coverage, added buffer base, pH, solvent, and solvent H\n 2<\/jats:sub>\n O\/D\n 2<\/jats:sub>\n O isotope effects. In the nonaqueous solvent, propylene carbonate, there is evidence for a role for surface-bound phosphonate groups as proton acceptors.\n <\/jats:p>","DOI":"10.1073\/pnas.1115769108","type":"journal-article","created":{"date-parts":[[2011,12,13]],"date-time":"2011-12-13T00:15:49Z","timestamp":1323735349000},"update-policy":"https:\/\/doi.org\/10.1073\/pnas.cm10313","source":"Crossref","is-referenced-by-count":48,"title":["Proton-coupled electron transfer at modified electrodes by multiple pathways"],"prefix":"10.1073","volume":"108","author":[{"given":"Zuofeng","family":"Chen","sequence":"first","affiliation":[{"name":"Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, NC 27599"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Aaron K.","family":"Vannucci","sequence":"additional","affiliation":[{"name":"Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, NC 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