The reduction of dioxygen by keggin heteropolytungstates

Ophir Snir, Yifeng Wang, Ira A. Weinstock

Research output: Contribution to journalReview articlepeer-review

5 Scopus citations


Reversible redox chemistries are an inherent feature of numerous metal oxide cluster anions (POMs). Moreover, as discrete molecular structures with well-defined and controllable solution chemistries, POMs can be deployed as physicochemical probes for studying inorganic reaction mechanisms. In the past decade, we have used an iso-structural series of α-Keggin heteropolytungstate cluster anions to systematically investigate a number of fundamental topics, including electron transfer to dioxygen. The iso-structural series of cluster anions is obtained by varying the heteroatom, Xn+, in the plenary, Td-symmetry α-Keggin ion, Xn+W 12O40(8-n)-, from Al3+ to Si 4+ to P5+. This results in a stepwise and linear modulation of ion charge and reduction potential, whose concerted effects on reaction rates can be used to better understand electron-transfer processes. Starting from the acquisition of activation parameters associated with electron self-exchange between the POMs themselves, the studies discussed in this review provide a detailed account of electron transfer from reduced α-Keggin heteropolytungstate anions to dioxygen, culminating in the recent discovery of a fundamentally new mechanism for electron transfer to O2 in water.

Original languageEnglish
Pages (from-to)247-258
Number of pages12
JournalIsrael Journal of Chemistry
Issue number2
StatePublished - 1 Feb 2011


  • cpet
  • dioxygen
  • electron transfer
  • polyoxometalates

ASJC Scopus subject areas

  • General Chemistry


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