4.7 Article

Protonation of a Peroxodiiron(III) Complex and Conversion to a Diiron(III/IV) Intermediate: Implications for Proton-Assisted O-O Bond Cleavage in Nonheme Diiron Enzymes

期刊

INORGANIC CHEMISTRY
卷 51, 期 19, 页码 10417-10426

出版社

AMER CHEMICAL SOC
DOI: 10.1021/ic301642w

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资金

  1. NIH [GM38767, EB001475]
  2. NSF Grant [CHE-1012485]
  3. NIH Postdoctoral Fellowship [ES017390]
  4. DOE Office of Biological and Environmental Research
  5. National Institutes of Health, National Center for Research Resources, Biomedical Technology Program [P41RR001209]
  6. Division Of Chemistry
  7. Direct For Mathematical & Physical Scien [1012485] Funding Source: National Science Foundation

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Oxygenation of a diiron(II) complex, [Fe-2(II)(mu-OH)(2)(BnBQA)(2)(NCMe)(2)](2+) [2, where BnBQA is N-benzyl-N,N-bis(2-quinolinylmethyl)amine], results in the formation of a metastable peroxocliferric intermediate, 3. The treatment of 3 with strong acid affords its conjugate acid, 4, in which the (mu-oxo)(mu-1,2-peroxo)diiron(III) core of 3 is protonated at the oxo bridge. The core structures of 3 and 4 are characterized in detail by UV-vis, Mossbauer, resonance Raman, and X-ray absorption spectroscopies. Complex 4 is shorter-lived than 3 and decays to generate in similar to 20% yield of a diiron(III/IV) species 5, which can be identified by electron paramagnetic resonance and Mossbauer spectroscopies. This reaction sequence demonstrates for the first time that protonation of the oxo bridge of a (mu-oxo)(mu-1,2-peroxo)diiron(III) complex leads to cleavage of the peroxo O-O bond and formation of a high-valent diiron complex, thereby mimicking the steps involved in the formation of intermediate X in the activation cycle of ribonucleotide reductase.

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