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Gimbert-Suriñach, Carolina; Moonshiram, Dooshaye; Francàs, Laia; Planas, Nora; Bernales, Varinia; Bozoglian, Fernando; Guda, Alexander; Mognon, Lorenzo; López, Isidoro; Hoque, Md Asmaul; Gagliardi, Laura; Cramer, Christopher J; Llobet, Antoni
Journal of the American Chemical Society, 11/2016, Letnik: 138, Številka: 47Journal Article
An end-on superoxido complex with the formula {CoIII(OH2)(trpy)CoIII(OO•)(trpy)(μ-bpp)}4+ (3 4+) (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+ (1 3+). DFT calculations agree with and complement the experimental data, offering a complete description of the transition states and intermediates involved in the catalytic cycle.
