Kinetic and thermodynamic parameters of copper-dioxygen interaction with different oxygen binding modes

Kenneth D. Karlin, William B Tolman, Susan Kaderli, Andreas D. Zuberbühler

Research output: Contribution to journalArticle

26 Scopus citations

Abstract

Kinetic and thermodynamic parameters for metal ion-O2 interaction have been obtained for a variety of copper(I) complexes with different binding modes for dioxygen. In general, favorable binding enthalpies of up to 80 kJ mol-1 are compensated by strongly negative reaction entropies up to -220 J K-1 mol-1 restricting the range of overall stabilities. Sequential formation of superoxo and peroxo complexes, as well as concomitant formation of η11 and η22 μ-peroxo complexes has been established by low-temperature stopped-flow experiments. In several cases, pseudoreversible binding of dioxygen is followed by an irreversible oxidation of the organic ligand. A recent result is the identification of a rapid equilibrium between an η22 μ-peroxo complex and the isomeric bis-μ oxo compound with broken O-O bond which may be fundamental to several O2 dependent redox enzymes.

Original languageEnglish (US)
Pages (from-to)215-222
Number of pages8
JournalJournal of Molecular Catalysis A: Chemical
Volume117
Issue number1-3
DOIs
StatePublished - Mar 14 1997

Keywords

  • Activation parameters
  • Copper complexes
  • Copper protein models
  • Dioxygen binding
  • Dioxygen carriers
  • Stoppped-flow kinetics

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