Dioxygen activation by copper sites: Relative stability and reactivity of (μ-η22-peroxo)- and bis(μ-oxo)dicopper cores

P. L. Holland, William B Tolman

Research output: Contribution to journalArticlepeer-review

143 Scopus citations


Investigations of complexes comprising the title cores are summarized with a view toward understanding their interconversion and possible implications in metallobiochemistry. Detailed studies on the solvent and concentration dependence of the equilibrium between (μ-η22-peroxo)dicopper(II) (A) and bis(μ-oxo)dicopper(III) (B) cores using mono- and binucleating ligands have elucidated the effects of ligand geometry, solubility, solvent donor ability and temperature on O-O bond cleavage and formation. These effects suggest that similar environmental influences may be significant in metalloenzymes and in particular, raise the possibility of either core being responsible for arene hydroxylation by tyrosinase. Recent studies on a synthetic system composed of a [Cu2(μ-O)2]2+ unit ligated to a mixed imine/amine ligand with an appended arene substituent substantiate the notion that core A or B may be competent in performing arene hydroxylation chemistry. (C) 1999 Elsevier Science S.A.

Original languageEnglish (US)
Pages (from-to)855-869
Number of pages15
JournalCoordination Chemistry Reviews
StatePublished - 1999

Bibliographical note

Funding Information:
We thank the contributors to the work described here that are cited in the references; their efforts are greatly appreciated. Financial support was provided by the National Institutes of Health, the National Science Foundation, the Searle Scholars—Chicago Community Trust, the Alfred P. Sloan and Camille & Henry Dreyfus Foundations, and the University of Minnesota.


  • Copper
  • Dioxygen
  • Synthetic models
  • Tyrosinase


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