Transition metal complexes and the activation of dioxygen

Gereon Wuu-Yee, William B Tolman

Research output: Contribution to journalArticlepeer-review

34 Scopus citations


In order to address how diverse metalloprotein active sites, in particular those containing iron and copper, guide O2 binding and activation processes to perform diverse functions, studies of synthetic models of the active sites have been performed. These studies have led to deep, fundamental chemical insights into how O2 coordinates to mono- and multinuclear Fe and Cu centers and is reduced to superoxo, peroxo, hydroperoxo, and, after O-O bond scission, oxo species relevant to proposed intermediates in catalysis. Recent advances in understanding the various factors that influence the course of O2 activation by Fe and Cu complexes are surveyed, with an emphasis on evaluating the structure, bonding, and reactivity of intermediates involved. The discussion is guided by an overarching mechanistic paradigm, with differences in detail due to the involvement of disparate metal ions, nuclearities, geometries, and supporting ligands providing a rich tapestry of reaction pathways by which O2 is activated at Fe and Cu sites.

Original languageEnglish (US)
Pages (from-to)131-204
Number of pages74
JournalMetal Ions in Life Sciences
StatePublished - 2015

Bibliographical note

Publisher Copyright:
© 2015 Springer International Publishing Switzerland.


  • copper
  • iron
  • oxo complexes
  • peroxo
  • superoxo


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