Nitrous-acid-mediated synthesis of iron-nitrosyl-porphyrin: pH-dependent release of nitric oxide

Chem Asian J. 2012 Nov;7(11):2690-5. doi: 10.1002/asia.201200518. Epub 2012 Aug 23.

Abstract

Two iron-nitrosyl-porphyrins, nitrosyl[meso-tetrakis(3,4,5-trimethoxyphenylporphyrin]iron(II) acetic acid solvate (3) and nitrosyl[meso-tetrakis(4-methoxyphenylporphyrin]iron(II) CH(2)Cl(2) solvate (4), were synthesized in quantitative yield by using a modified procedure with nitrous acid, followed by oxygen-atom abstraction by triphenylphosphine under an argon atmosphere. These nitrosyl porphyrins are in the {FeNO}(7) class. Under an argon atmosphere, these compounds are relatively stable over a broad range of pH values (4-8) but, under aerobic conditions, they release nitric oxide faster at high pH values than that at low pH values. The generated nitric-oxide-free iron(III)-porphyrin can be re-nitrosylated by using nitrous acid and triphenylphosphine. The rapid release of NO from these Fe(II) complexes at high pH values seems to be similar to that in nitrophorin, a nitric-oxide-transport protein, which formally possesses Fe(III). However, because the release of NO occurs from ferrous-nitrosyl-porphyrin under aerobic conditions, these compounds are more closely related to nitrobindin, a recently discovered heme protein.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Argon / chemistry
  • Coordination Complexes / chemistry
  • Crystallography, X-Ray
  • Electron Spin Resonance Spectroscopy
  • Hydrogen-Ion Concentration
  • Metalloporphyrins / chemistry*
  • Molecular Conformation
  • Nitric Oxide / chemistry*
  • Nitrous Acid / chemistry*
  • Organophosphorus Compounds / chemistry

Substances

  • Coordination Complexes
  • Metalloporphyrins
  • Organophosphorus Compounds
  • nitrosyl(meso-tetrakis(3,4,5-trimethoxyphenylporphyrin))iron(II)
  • nitrosyl(meso-tetrakis(4-methoxyphenylporphyrin))iron(II)
  • ferroporphyrin
  • triphenylphosphine
  • Nitric Oxide
  • Argon
  • Nitrous Acid