JBIC Journal of Biological Inorganic Chemistry

, Volume 21, Issue 5–6, pp 745–755 | Cite as

The secondary coordination sphere and axial ligand effects on oxygen reduction reaction by iron porphyrins: a DFT computational study

  • Takehiro OhtaEmail author
  • Perumandla Nagaraju
  • Jin-Gang Liu
  • Takashi Ogura
  • Yoshinori Naruta
Original Paper
Part of the following topical collections:
  1. E.I. Solomon: Papers in Celebration of His 2016 ACS Alfred Bader Award in Bioorganic or Bioinorganic Chemistry


Oxygen reduction reaction (ORR) catalyzed by a bio-inspired iron porphyrin bearing a hanging carboxylic acid group over the porphyrin ring, and a tethered axial imidazole ligand was studied by DFT calculations. BP86 free energy calculations of the redox potentials and pK a’s of reaction components involved in the proton coupled electron transfer (PCET) reactions of the ferric-hydroxo and -superoxo complexes were performed based on Born–Haber thermodynamic cycle in conjunction with a continuum solvation model. The comparison was made with iron porphyrins that lack either in the hanging acid group or axial ligand, suggesting that H-bond interaction between the carboxylic acid and iron-bound hydroxo, aquo, superoxo, and peroxo ligands (de)stabilizes the Fe–O bonding, resulting in the increase in the reduction potential of the ferric complexes. The axial ligand interaction with the imidazole raises the affinity of the iron-bound superoxo and peroxo ligands for proton. In addition, a low-spin end-on ferric-hydroperoxo intermediate, a key precursor for O–O cleavage, can be stabilized in the presence of axial ligation. Thus, selective and efficient ORR of iron porphyrin can be achieved with the aid of the secondary coordination sphere and axial ligand interactions.


Computational chemistry Density functional theory Dioxygen Heme Model compound Porphyrin Electrochemistry 



This work was financially supported by Scientific Research (C) (No. 24550080) and Scientific Research on Innovative Area (No. 25109535) to T.O. from JSPS and by the Elemental Science and Technology Project to Y.N. from the MEXT of Japan. NP thanks the Mitsubishi UFJ Trust Scholarship. JGL is grateful to the NSF of China (No. 21271072, 21571062), the Program for Professor of Special Appointment (Eastern Scholar) at Shanghai Institutions of Higher Learning.

Supplementary material

775_2016_1380_MOESM1_ESM.pdf (1.7 mb)
Supplementary material 1 (PDF 1760 kb)


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Copyright information

© SBIC 2016

Authors and Affiliations

  • Takehiro Ohta
    • 1
    • 4
    Email author
  • Perumandla Nagaraju
    • 2
    • 4
  • Jin-Gang Liu
    • 3
  • Takashi Ogura
    • 1
  • Yoshinori Naruta
    • 2
    • 4
  1. 1.Picobiology Institute, Graduate School of Life ScienceUniversity of Hyogo, RSC-UH LP CenterHyogoJapan
  2. 2.Institute of Science and Technology ResearchChubu UniversityKasugaiJapan
  3. 3.Department of ChemistryEast China University of Science and TechnologyShanghaiChina
  4. 4.Institute for Materials Chemistry and EngineeringKyushu UniversityFukuokaJapan

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