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

49 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

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

year = "2016",

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doi = "10.1021/jacs.6b08532",

language = "English (US)",

volume = "138",

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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

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

Abstract

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