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Oxygen activation by mononuclear Mn, Co, and Ni centers in biology and synthetic complexes

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Abstract

The active sites of metalloenzymes that catalyze O2-dependent reactions generally contain iron or copper ions. However, several enzymes are capable of activating O2 at manganese or nickel centers instead, and a handful of dioxygenases exhibit activity when substituted with cobalt. This minireview summarizes the catalytic properties of oxygenases and oxidases with mononuclear Mn, Co, or Ni active sites, including oxalate-degrading oxidases, catechol dioxygenases, and quercetin dioxygenase. In addition, recent developments in the O2 reactivity of synthetic Mn, Co, or Ni complexes are described, with an emphasis on the nature of reactive intermediates featuring superoxo-, peroxo-, or oxo-ligands. Collectively, the biochemical and synthetic studies discussed herein reveal the possibilities and limitations of O2 activation at these three “overlooked” metals.

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Acknowledgements

The authors gratefully acknowledge financial support from the U.S. National Science Foundation (CHE-1056845) and Marquette University.

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  1. Department of Chemistry, Marquette University, Milwaukee, WI, 53201, USA

    Adam T. Fiedler & Anne A. Fischer

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  1. Adam T. Fiedler
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Correspondence to Adam T. Fiedler.

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Fiedler, A.T., Fischer, A.A. Oxygen activation by mononuclear Mn, Co, and Ni centers in biology and synthetic complexes. J Biol Inorg Chem 22, 407–424 (2017). https://doi.org/10.1007/s00775-016-1402-7

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