Formation of superoxide-metal ion complexes and the electron transfer catalysis

Shunichi Fukuzumi, Hideki Ohtsu, Kei Ohkubo, Shinobu Itoh, Hiroshi Imahori

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Abstract

The formation of a variety of superoxide-metal complexes and their catalytic functions have been reviewed. The g==-values of the EPR spectra of superoxide-metal ion complexes vary significantly depending on the type of metal ions. From the deviation of the g==-value from the free spin value are determined the energy splitting values (ΔE) of πg levels due to complex formation. The ΔE values correlate well with the catalytic reactivities of the metal ions in the electron transfer reduction of oxygen. Such a complex formation between superoxide ion and metal ions has been shown to play an essential role in the enzymatic function of superoxide dismutase, formation of active oxygen-copper complexes and the novel catalytic effect of O2 in back electron transfer of zinc porphyrin-fullerene linked molecules.

Original languageEnglish
Pages (from-to)71-80
Number of pages10
JournalCoordination Chemistry Reviews
Volume226
Issue number1-2
DOIs
StatePublished - 2002

Bibliographical note

Funding Information:
The authors are deeply indebted to the work of all collaborators and coworkers whose names are listed in the references. S.F. acknowledges continuous support of the Ministry of Education, Science, Culture and Sports, Japan (a Grant-in-Aid for Scientific Research Priority Area, No. 11228205).

Keywords

  • Back electron transfer
  • Catalysis
  • Metal ion
  • Superoxide dismutase
  • Superoxide ion

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