Structural and Spectroscopic Characterization of Reaction Intermediates Involved in a Dinuclear Co-Hbpp Water Oxidation Catalyst

Carolina Gimbert-Suriñach, Dooshaye Moonshiram, Laia Francàs, Nora Planas, Varinia Bernales, Fernando Bozoglian, Alexander Guda, Lorenzo Mognon, Isidoro López, Md Asmaul Hoque, Laura Gagliardi, Christopher J. Cramer, Antoni Llobet

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Abstract

An end-on superoxido complex with the formula {[CoIII(OH2)(trpy)][CoIII(OO)(trpy)](μ-bpp)}4+ (34+) (bpp- = bis(2-pyridyl)-3,5-pyrazolate; trpy = 2,2′6′:2″-terpyridine) has been characterized by resonance Raman, electron paramagnetic resonance, and X-ray absorption spectroscopies. These results together with online mass spectrometry experiments using 17O and 18O isotopically labeled compounds prove that this compound is a key intermediate of the water oxidation reaction catalyzed by the peroxido-bridged complex {[CoIII(trpy)]2(μ-bpp)(μ-OO)}3+ (13+). DFT calculations agree with and complement the experimental data, offering a complete description of the transition states and intermediates involved in the catalytic cycle.

Original languageEnglish (US)
Pages (from-to)15291-15294
Number of pages4
JournalJournal of the American Chemical Society
Volume138
Issue number47
DOIs
StatePublished - Nov 30 2016

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    Gimbert-Suriñach, C., Moonshiram, D., Francàs, L., Planas, N., Bernales, V., Bozoglian, F., Guda, A., Mognon, L., López, I., Hoque, M. A., Gagliardi, L., Cramer, C. J., & Llobet, A. (2016). Structural and Spectroscopic Characterization of Reaction Intermediates Involved in a Dinuclear Co-Hbpp Water Oxidation Catalyst. Journal of the American Chemical Society, 138(47), 15291-15294. https://doi.org/10.1021/jacs.6b08532