Structural and Spectroscopic Characterization of Reaction Intermediates Involved in a Dinuclear Co–Hbpp Water Oxidation Catalyst
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- 作者：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
- 刊名：Journal of the American Chemical Society
- 出版年：2016
- 出版时间：November 30, 2016
- 年：2016
- 卷：138
- 期：47
- 页码：15291-15294
- 全文大小：346K
- ISSN：1520-5126
文摘
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.