Heme/non-heme diiron(II) complexes and O2, CO, and NO adducts as reduced and substrate-bound models for the active site of bacterial nitric oxide reductase

J Am Chem Soc. 2005 Mar 16;127(10):3310-20. doi: 10.1021/ja0458773.

Abstract

As a first generation model for the reactive reduced active-site form of bacterial nitric oxide reductase, a heme/non-heme diiron(II) complex [(6L)Fe(II)...Fe(II)-(Cl)]+ (2) {where 6L = partially fluorinated tetraphenylporphyrin with a tethered tetradentate TMPA chelate; TMPA = tris(2-pyridyl)amine} was generated by reduction of the corresponding mu-oxo diferric compound [(6L)Fe(III)-O-Fe(III)-Cl]+ (1). Coordination chemistry models for reactions of reduced NOR with O2, CO, and NO were also developed. With O2 and CO, adducts are formed, [(6L)Fe(III)(O2-))(thf)...Fe(II)-Cl]B(C6F5)4 (2a x O2) {lambda(max) 418 (Soret), 536 nm; nu(O-O) = 1176 cm(-1), nu(Fe-O) = 574 cm(-1) and [(6L)Fe(II)(CO)(thf)Fe(II)-Cl]B(C6F5)4 (2a x CO) {nu(CO) 1969 cm(-1)}, respectively. Reaction of purified nitric oxide with 2 leads to the dinitrosyl complex [(6L)Fe(NO)Fe(NO)-Cl]B(C6F5)4 (2a x (NO)2) with nu(NO) absorptions at 1798 cm(-1) (non-heme Fe-NO) and 1689 cm(-1) (heme-NO).

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, U.S. Gov't, P.H.S.

MeSH terms

  • Binding Sites
  • Biomimetic Materials / chemical synthesis
  • Biomimetic Materials / chemistry
  • Biomimetic Materials / metabolism
  • Carbon Monoxide / chemistry
  • Carbon Monoxide / metabolism
  • Ferrous Compounds / chemical synthesis
  • Ferrous Compounds / chemistry*
  • Ferrous Compounds / metabolism
  • Heme / chemistry*
  • Heme / metabolism
  • Iron Chelating Agents / chemistry
  • Magnetic Resonance Spectroscopy
  • Nitric Oxide / chemistry
  • Nitric Oxide / metabolism
  • Oxidoreductases / chemistry*
  • Oxidoreductases / metabolism
  • Oxygen / chemistry
  • Oxygen / metabolism
  • Porphyrins / chemistry
  • Pyridines / chemistry
  • Spectroscopy, Fourier Transform Infrared
  • Spectrum Analysis, Raman

Substances

  • Ferrous Compounds
  • Iron Chelating Agents
  • Porphyrins
  • Pyridines
  • tetraphenylporphyrin
  • tris(2-pyridylmethyl)amine
  • Nitric Oxide
  • Heme
  • Carbon Monoxide
  • Oxidoreductases
  • nitric-oxide reductase
  • Oxygen