A Nonheme Mononuclear {FeNO}7 Complex that Produces N2O in the Absence of an Exogenous Reductant

Aniruddha Dey, Jesse B. Gordon, Therese Albert, Sinan Sabuncu, Maxime A. Siegler, Samantha N. MacMillan, Kyle M. Lancaster, Pierre Moënne-Loccoz, David P. Goldberg

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9 Scopus citations


A new nonheme iron(II) complex, FeII(Me3TACN)((OSiPh2)2O) (1), is reported. Reaction of 1 with NO(g) gives a stable mononitrosyl complex Fe(NO)(Me3TACN)((OSiPh2)2O) (2), which was characterized by Mössbauer (δ=0.52 mm s−1, |ΔEQ|=0.80 mm s−1), EPR (S=3/2), resonance Raman (RR) and Fe K-edge X-ray absorption spectroscopies. The data show that 2 is an {FeNO}7 complex with an S=3/2 spin ground state. The RR spectrum (λexc=458 nm) of 2 combined with isotopic labeling (15N, 18O) reveals ν(N-O)=1680 cm−1, which is highly activated, and is a nearly identical match to that seen for the reactive mononitrosyl intermediate in the nonheme iron enzyme FDPnor (ν(NO)=1681 cm−1). Complex 2 reacts rapidly with H2O in THF to produce the N-N coupled product N2O, providing the first example of a mononuclear nonheme iron complex that is capable of converting NO to N2O in the absence of an exogenous reductant.

Original languageEnglish (US)
Pages (from-to)21558-21564
Number of pages7
JournalAngewandte Chemie - International Edition
Issue number39
StatePublished - Sep 20 2021


  • iron
  • nitric oxide
  • nitrous oxide
  • nonheme
  • reduction

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)


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