Speciation of the catalytic oxygen evolution system

[Mn III/IV2(μ-O)2(terpy)2(H 2O)2](NO3)3 + HSO5 -

Hongyu Chen, Ranitendranath Tagore, Gerard Olack, John S. Vrettos, Tsu Chien Weng, James Penner-Hahn, Robert H. Crabtree, Gary W Brudvig

Research output: Contribution to journalArticle

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Abstract

[MnIII/IV2(μ-O)2(terpy) 2(OH2)2](NO3)3 (1, where terpy = 2,2′:6′2″-terpyridine) + oxone (2KHSO 5·KHSO4·K2SO4) provides a functional model system for the oxygen-evolving complex of photosystem II that is based on a structurally relevant Mn-(μ-O) 2-Mn moiety (Limburg, J.; et al. J. Am. Chem. Soc. 2001, 123, 423-430). In this study, electron paramagnetic resonance, ultraviolet-visible spectroscopy, electrospray ionization mass spectrometry, X-ray absorption spectroscopy, and gas-phase stable isotope ratio mass spectrometry were utilized to identify the title compounds in the catalytic solution. We find that (a) O2 evolution does not proceed through heterogeneous catalysis by MnO2 or other decomposition products, that (b) O atoms from solvent water are incorporated into the evolved O2 to a significant extent but not into oxone, that (c) the MnIII/IV2 title compound 1 is an active precatalyst in the catalytic cycle of O2 evolution with oxone, while the MnIV/IV2 oxidation state is not, and that (d) the isotope label incorporation in the evolved O2, together with points a-c above, is consistent with a mechanism involving competing reactions of oxone and water with a "MnV=O" intermediate in the O-O bond-forming step.

Original languageEnglish
Pages (from-to)34-43
Number of pages10
JournalInorganic Chemistry
Volume46
Issue number1
DOIs
Publication statusPublished - Jan 8 2007

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mass spectroscopy
Oxygen
isotope ratios
oxygen
Isotopes
water
catalysis
Mass spectrometry
electron paramagnetic resonance
absorption spectroscopy
isotopes
vapor phases
decomposition
ionization
Electrospray ionization
oxidation
cycles
X ray absorption spectroscopy
Photosystem II Protein Complex
Water

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Speciation of the catalytic oxygen evolution system : [Mn III/IV2(μ-O)2(terpy)2(H 2O)2](NO3)3 + HSO5 -. / Chen, Hongyu; Tagore, Ranitendranath; Olack, Gerard; Vrettos, John S.; Weng, Tsu Chien; Penner-Hahn, James; Crabtree, Robert H.; Brudvig, Gary W.

In: Inorganic Chemistry, Vol. 46, No. 1, 08.01.2007, p. 34-43.

Research output: Contribution to journalArticle

Chen, H, Tagore, R, Olack, G, Vrettos, JS, Weng, TC, Penner-Hahn, J, Crabtree, RH & Brudvig, GW 2007, 'Speciation of the catalytic oxygen evolution system: [Mn III/IV2(μ-O)2(terpy)2(H 2O)2](NO3)3 + HSO5 -', Inorganic Chemistry, vol. 46, no. 1, pp. 34-43. https://doi.org/10.1021/ic060499j
Chen, Hongyu ; Tagore, Ranitendranath ; Olack, Gerard ; Vrettos, John S. ; Weng, Tsu Chien ; Penner-Hahn, James ; Crabtree, Robert H. ; Brudvig, Gary W. / Speciation of the catalytic oxygen evolution system : [Mn III/IV2(μ-O)2(terpy)2(H 2O)2](NO3)3 + HSO5 -. In: Inorganic Chemistry. 2007 ; Vol. 46, No. 1. pp. 34-43.
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