High-valent nonheme iron. Two distinct iron(IV) species derived from a common iron(II) precursor

Michael P. Jensen, Miquel Costas, Raymond Y.N. Ho, József Kaizer, Antoni Mairata I Payeras, Eckard Münck, Lawrence Que, Jan Uwe Ronde, Audria Stubna

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104 Citations (Scopus)

Abstract

The reaction of [FeII(β-BPMCN)(OTf)2] (1, BPMCN = N,N′-bis(2-pyridylmethyl)-N,N′-dimethyl-trans-1,2- diaminocyclohexane) with tBuOOH at low-temperature yields alkylperoxoiron(III) intermediates 2 in CH2Cl2 and 2-NCMe in CH3CN. At -45 °C and above, 2-NCMe converts to a pale green species 3 (λmax = 753 nm, ε = 280 M-1 cm -1) in 90% yield, identified as [FeIV(O)(BPMCN)(NCCH 3)]2+ by comparison to other nonheme [Fe IV(O)(L)]2+ complexes. Below -55 °C in CH 2Cl2, 2 decays instead to form deep turquoise 4 (λmax = 656, 845 nm; ε = 4000, 3600 M-1 cm-1), formulated to be an unprecedented alkylperoxoiron(IV) complex [FeIV(BPMCN)(OH)(OOtBu)]2+ on the basis of Mössbauer, EXAFS, resonance Raman, NMR, and mass spectral evidence. The reactivity of 1 with tBuOOH in the two solvents reveals an unexpectedly rich iron(IV) chemistry that can be supported by the BPMCN ligand.

Original languageEnglish
Pages (from-to)10512-10525
Number of pages14
JournalJournal of the American Chemical Society
Volume127
Issue number30
DOIs
Publication statusPublished - Aug 3 2005

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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    Jensen, M. P., Costas, M., Ho, R. Y. N., Kaizer, J., Mairata I Payeras, A., Münck, E., Que, L., Ronde, J. U., & Stubna, A. (2005). High-valent nonheme iron. Two distinct iron(IV) species derived from a common iron(II) precursor. Journal of the American Chemical Society, 127(30), 10512-10525. https://doi.org/10.1021/ja0438765