Secondary coordination sphere influence on the reactivity of nonheme iron(II) complexes: An experimental and DFT approach

Sumit Sahu, Leland R. Widger, Matthew G. Quesne, Sam P. De Visser, Hirotoshi Matsumura, Pierre Moënne-Loccoz, Maxime A. Siegler, David P. Goldberg

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The new biomimetic ligands N4Py2Ph (1) and N4Py 2Ph,amide (2) were synthesized and yield the iron(II) complexes [FeII(N4Py2Ph)(NCCH3)](BF4) 2 (3) and [FeII(N4Py2Ph,amide)](BF 4)2 (5). Controlled orientation of the Ph substituents in 3 leads to facile triplet spin reactivity for a putative FeIV(O) intermediate, resulting in rapid arene hydroxylation. Addition of a peripheral amide substituent within hydrogen-bond distance of the iron first coordination sphere leads to stabilization of a high-spin FeIIIOOR species which decays without arene hydroxylation. These results provide new insights regarding the impact of secondary coordination sphere effects at nonheme iron centers.

Original languageEnglish (US)
Pages (from-to)10590-10593
Number of pages4
JournalJournal of the American Chemical Society
Issue number29
StatePublished - Jul 24 2013


ASJC Scopus subject areas

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

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