Nitrite activation to nitric oxide via one-fold protonation of iron(II)-O,O-nitrito complex: relevance to the nitrite reductase activity of deoxyhemoglobin and deoxyhemerythrin

J Am Chem Soc. 2013 Dec 18;135(50):18758-61. doi: 10.1021/ja4105864. Epub 2013 Dec 5.

Abstract

The reversible transformations [(Bim)3Fe(κ(2)-O2N)][BF4] (3) <-> [(Bim)3Fe(NO)(κ(1)-ONO)][BF4]2 (4) were demonstrated and characterized. Transformation of O,O-nitrito-containing complex 3 into [(Bim)3Fe(μ-O)(μ-OAc)Fe(Bim)3](3+) (5) along with the release of NO and H2O triggered by 1 equiv of AcOH implicates that nitrite-to-nitric oxide conversion occurs, in contrast to two protons needed to trigger nitrite reduction producing NO observed in the protonation of [Fe(II)-nitro] complexes.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Ferrous Compounds / chemistry*
  • Hemerythrin / chemistry*
  • Hemoglobins / chemistry*
  • Nitric Oxide / chemistry*
  • Nitrite Reductases / chemistry*
  • Nitrites / chemistry*
  • Spectrum Analysis / methods

Substances

  • Ferrous Compounds
  • Hemerythrin
  • Hemoglobins
  • Nitrites
  • deoxyhemerythrin
  • Nitric Oxide
  • deoxyhemoglobin
  • Nitrite Reductases