Synthesis, molecular structure, and spectroelectrochemistry of a nitrosyl iron porphyrin containing an unsymmetrical xanthene-linked porphyrin core

Nan Xu, Douglas R. Powell, George B. Richter-Addo

Research output: Contribution to journalArticlepeer-review

3 Scopus citations

Abstract

Synthetic nitrosyl porphyrins with meso-aryl substituents are potential models for the biologically-important NO-bound P460 heme cofactor. A five-coordinate iron nitrosyl tetraaryl-porphyrin (HTPPX-CO2H)Fe(NO) containing a xanthene-based meso substituent has been prepared. The crystal structure of this formally {FeNO}7 complex reveals an ordered axial and bent NO ligand (∠FeNO = 142.5(6) Å) displaying an off-axis tilt of the nitrosyl N atom from the heme normal by 9.2. Surprisingly, the porphyrin core does not display the expected asymmetry in FeN(por) distances frequently observed in iron nitrosyl porphyrins. The redox behavior as determined by cyclic voltammetry reveals, in contrast to most (por)Fe(NO) compounds, a fast NO dissociation after electrooxidation in CH2Cl2 to result in a net chemically-irreversible oxidation at Epa = +0.77 V vs Ag/AgCl. IR spectroelectrochemistry reveals a recombination, on the spectroelectrochemistry time-scale, of the dissociated NO on oxidation with electrogenerated [(HTPPX-CO2H)Fe]+.

Original languageEnglish (US)
Pages (from-to)61-65
Number of pages5
JournalNitric Oxide - Biology and Chemistry
Volume37
Issue number1
DOIs
StatePublished - Feb 15 2014

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Physiology
  • Clinical Biochemistry
  • Cancer Research

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