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

doi:10.1021/jacs.6b08532

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

Research output: Contribution to journal › Article › peer-review

40 Scopus citations

Abstract

An end-on superoxido complex with the formula {[Co^III(OH₂)(trpy)][Co^III(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 {[Co^III(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 language	English (US)
Pages (from-to)	15291-15294
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	138
Issue number	47
DOIs	https://doi.org/10.1021/jacs.6b08532
State	Published - 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).

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© 2016 American Chemical Society.

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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

Gimbert-Suriñach, C, Moonshiram, D, Francàs, L, Planas, N, Bernales, V, Bozoglian, F, Guda, A, Mognon, L, López, I, Hoque, MA, Gagliardi, L , Cramer, CJ & 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, vol. 138, no. 47, pp. 15291-15294. https://doi.org/10.1021/jacs.6b08532

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

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.",

author = "Carolina Gimbert-Suri{\~n}ach and Dooshaye Moonshiram and Laia Franc{\`a}s and Nora Planas and Varinia Bernales and Fernando Bozoglian and Alexander Guda and Lorenzo Mognon and Isidoro L{\'o}pez and Hoque, {Md Asmaul} and Laura Gagliardi and Cramer, {Christopher J.} and Antoni Llobet",

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: {\textcopyright} 2016 American Chemical Society.",

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T1 - Structural and Spectroscopic Characterization of Reaction Intermediates Involved in a Dinuclear Co-Hbpp Water Oxidation Catalyst

AU - Gimbert-Suriñach, Carolina

AU - Moonshiram, Dooshaye

AU - Francàs, Laia

AU - Planas, Nora

AU - Bernales, Varinia

AU - Bozoglian, Fernando

AU - Guda, Alexander

AU - Mognon, Lorenzo

AU - López, Isidoro

AU - Hoque, Md Asmaul

AU - Gagliardi, Laura

AU - Cramer, Christopher J.

AU - Llobet, Antoni

N1 - 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.

PY - 2016/11/30

Y1 - 2016/11/30

N2 - 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.

AB - 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.

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JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

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ER -

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

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