Título:
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Structural and Spectroscopic Characterization of Reaction Intermediates Involved in a Dinuclear Co-Hbpp Water Oxidation Catalyst
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Autor/a:
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Gimbert-Suriñach, Carolina; Moonshiram, Dooshaye; Francas, Laia; Planas, Nora; Bernales, Varinia; Bozoglian, Fernando; Guda, Alexander; Mognon, Lorenzo; López, Isidoro; Hoque, Md Asmaul; Gagliardi, Laura; Cramer, Christopher J.; Llobet, Antoni
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Abstract:
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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. |
Fecha de creación:
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2016 |
Derechos:
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Copyright © 2016 American Chemical Society |
Tipo de documento:
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Artículo |
DOI:
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https://dx.doi.org/10.1021/jacs.6b08532
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Editor:
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American Chemical Society
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Publish at:
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Journal of the American Chemical Society
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Compartir:
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