C-H Oxidation by a Diiron Complex with Facially Opposing Active Sites

Stacey Lindsay, Sophie L. Mader, Ville R.I. Kaila, Corinna R. Hess

Research output: Contribution to journalArticlepeer-review

5 Scopus citations

Abstract

C−H oxidation is catalyzed by a high-spin ferrous dimer, [(L1)2Fe2(CH3CN)2](PF6)4 (1), that offers two identical functional sites, separated by > 7 Å. The complex provides a unique contrast to both mononuclear and binuclear non-heme enzyme active sites as well as biomimetic complexes. The oxidative activity of 1 was examined using a range of substrates (cyclohexene, 9,10-dihydroanthracene, xanthene, triphenylmethane, triphenylphosphine, and cyclohexane) and PhIO as an oxidant. The studies establish the O-atom transfer and H-atom abstraction ability of the diiron complex. We further probe the energetics of cyclohexene oxidation by 1 and derive putative mechanisms for the pathways of allylic alcohol and epoxide formation using density functional theory (DFT) calculations. The DFT calculations indicate that the oxidation reactions proceed via a FeIV=O species in the triplet state, and that both iron centers can act independently of each other. The combined results provide insight into hydrocarbon oxidation by non-coupled binuclear systems.

Original languageEnglish
Pages (from-to)1602-1608
Number of pages7
JournalChemistrySelect
Volume3
Issue number5
DOIs
StatePublished - 7 Feb 2018

Keywords

  • DFT
  • diiron
  • hydrocarbon oxidation
  • iron-oxo
  • non-heme

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