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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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
Issue number47
StatePublished - Nov 30 2016

Bibliographical note

Funding Information:
Financial support from MINECO and FEDER (CTQ-2016-80058-R, SEV-2013-0319, and CTQ-2014-52974-REDC) and EUCOSTActions CM1202 and CM1205 is acknowledged. D.M. thanks the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences (BES), CSGB Division (Contract DE-AC02-06CH11357) and resources of the Advanced Photon Source (APS) and Center of Nanoscale Materials both at Argonne National Laboratory (ANL). Dr. Sun from Sector 20 (APS), supported by U.S.DOEand the Canadian Light Source, is also acknowledged. C.J.C. thanks the U.S. NSF for support (CHE-1361595). L.G. was partially supported by the U.S. DOE, Basic Energy Sciences, under SciDAC (Grant No. DESC0008666). A.G. thanks the Russian Ministry of Education and Science for the financial support (Agreement No. 14.587.21.0002, unique identifier RFMEFI58714X0002).

Publisher Copyright:
© 2016 American Chemical Society.


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