@article{0286c52731fb4d33af0b9f7f8316e77a,
title = "A Nonheme Mononuclear {FeNO}7 Complex that Produces N2O in the Absence of an Exogenous Reductant",
abstract = "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 M{\"o}ssbauer (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.",
keywords = "iron, nitric oxide, nitrous oxide, nonheme, reduction",
author = "Aniruddha Dey and Gordon, {Jesse B.} and Therese Albert and Sinan Sabuncu and Siegler, {Maxime A.} and MacMillan, {Samantha N.} and Lancaster, {Kyle M.} and Pierre Mo{\"e}nne-Loccoz and Goldberg, {David P.}",
note = "Funding Information: The NSF (CHE1566007 and CHE1955527 to D.P.G.) and NIH (GM124908 to K.M.L. and GM074785 to P.M.L.) are gratefully acknowledged for financial support. J.B.G. would like to thank JHU for funding through the Sonneborn Fellowship. A.D. sincerely thanks Jessica Zarenkiewicz and Prof. J. P. Toscano (JHU Chemistry) as well as Zhuoqun Zhang and Prof. A. S. Hall (JHU Material Science & Engineering) for the use of GC/GC‐MS instrumentation (headspace gas analysis). XAS data were obtained at the Stanford Synchrotron Radiation Lightsource. Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE‐AC02‐76SF00515. The SSRL Structural Molecular Biology Program is supported by the DOE Office of Biological and Environmental Research, and by the National Institutes of Health, National Institute of General Medical Sciences (P30GM133894). Publisher Copyright: {\textcopyright} 2021 Wiley-VCH GmbH",
year = "2021",
month = sep,
day = "20",
doi = "10.1002/anie.202109062",
language = "English (US)",
volume = "60",
pages = "21558--21564",
journal = "Angewandte Chemie - International Edition",
issn = "1433-7851",
publisher = "John Wiley and Sons Ltd",
number = "39",
}