Non-Heme Diiron Model Complexes Can Mediate Direct NO Reduction

Mechanistic Insight into Flavodiiron NO Reductases

Hai T. Dong, Corey J. White, Bo Zhang, Carsten Krebs, Nicolai Lehnert

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

Flavodiiron nitric oxide reductases (FNORs), a common enzyme family found in various types of pathogenic bacteria, are capable of reducing nitric oxide (NO) to nitrous oxide (N2O) as a protective detoxification mechanism. Utilization of FNORs in pathogenic bacteria helps them survive and proliferate in the human body, thus causing chronic infections. In this paper, we present a new diiron model complex, [Fe2((Py2PhO2)MP)(OPr)2](OTf), with bridging propionate ligands (OPr-) that is capable of directly reducing NO to N2O in quantitative yield without the need to (super)reduce the complex. We first prepared the diferric precursor and characterized it by UV-vis, IR, NMR and Mössbauer spectroscopies, cyclic voltammetry, and mass spectrometry. This complex can then conveniently be reduced to the diferrous complex using CoCp2. Even though this diferrous complex is highly reactive, we have successfully isolated and characterized this species using X-ray crystallography and various spectroscopic techniques. Most importantly, upon reacting this diferrous complex with NO gas, we observe quantitative formation of N2O via IR gas headspace analysis, the first demonstration of direct NO reduction by a non-heme diiron model complex. This finding directly supports recent mechanistic proposals for FNORs.

Original languageEnglish (US)
Pages (from-to)13429-13440
Number of pages12
JournalJournal of the American Chemical Society
Volume140
Issue number41
DOIs
StatePublished - Oct 17 2018

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Nitric oxide
Nitric Oxide
Bacteria
Gases
Detoxification
Gas fuel analysis
X ray crystallography
X Ray Crystallography
Propionates
Nitrous Oxide
Human Body
Cyclic voltammetry
Mass spectrometry
Mass Spectrometry
Magnetic Resonance Spectroscopy
Demonstrations
Nuclear magnetic resonance
Spectroscopy
Ligands
nitric-oxide reductase

All Science Journal Classification (ASJC) codes

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

Cite this

@article{f95372513a9a4ecbaf478b8729a55301,
title = "Non-Heme Diiron Model Complexes Can Mediate Direct NO Reduction: Mechanistic Insight into Flavodiiron NO Reductases",
abstract = "Flavodiiron nitric oxide reductases (FNORs), a common enzyme family found in various types of pathogenic bacteria, are capable of reducing nitric oxide (NO) to nitrous oxide (N2O) as a protective detoxification mechanism. Utilization of FNORs in pathogenic bacteria helps them survive and proliferate in the human body, thus causing chronic infections. In this paper, we present a new diiron model complex, [Fe2((Py2PhO2)MP)(OPr)2](OTf), with bridging propionate ligands (OPr-) that is capable of directly reducing NO to N2O in quantitative yield without the need to (super)reduce the complex. We first prepared the diferric precursor and characterized it by UV-vis, IR, NMR and M{\"o}ssbauer spectroscopies, cyclic voltammetry, and mass spectrometry. This complex can then conveniently be reduced to the diferrous complex using CoCp2. Even though this diferrous complex is highly reactive, we have successfully isolated and characterized this species using X-ray crystallography and various spectroscopic techniques. Most importantly, upon reacting this diferrous complex with NO gas, we observe quantitative formation of N2O via IR gas headspace analysis, the first demonstration of direct NO reduction by a non-heme diiron model complex. This finding directly supports recent mechanistic proposals for FNORs.",
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Non-Heme Diiron Model Complexes Can Mediate Direct NO Reduction : Mechanistic Insight into Flavodiiron NO Reductases. / Dong, Hai T.; White, Corey J.; Zhang, Bo; Krebs, Carsten; Lehnert, Nicolai.

In: Journal of the American Chemical Society, Vol. 140, No. 41, 17.10.2018, p. 13429-13440.

Research output: Contribution to journalArticle

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T2 - Mechanistic Insight into Flavodiiron NO Reductases

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AU - Krebs, Carsten

AU - Lehnert, Nicolai

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