How useful are vibrational frequencies of isotopomeric O2 fragments for assessing local symmetry? Some simple systems and the vexing case of a galactose oxidase model

Christopher R. Kinsinger, Benjamin F. Gherman, Laura Gagliardi, Christopher J. Cramer

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25 Scopus citations

Abstract

The tendency for mixed-isotope O2 fragments to exhibit different stretching frequencies in asymmetric environments is examined with various levels of electronic structure theory for simple peroxides and peroxyl radicals, as well as for a variety of monocopper-O2 complexes. The study of the monocopper species is motivated by their relevance to the active site of galactose oxidase. Extensive theoretical work with an experimental model characterized by Jazdzewski et al. (J. Biol. Inorg. Chem. 8:381-393, 2003) suggests that the failure to observe a splitting between 16O 18O and 18O16O isotopomers cannot be taken as evidence against end-on O2 coordination. Conformational analysis on an energetic basis, however, is complicated by biradical character inherent in all of the copper-O2 singlet structures.

Original languageEnglish (US)
Pages (from-to)778-789
Number of pages12
JournalJournal of Biological Inorganic Chemistry
Volume10
Issue number7
DOIs
StatePublished - Nov 2005

Bibliographical note

Funding Information:
Acknowledgements This work was supported by the National Science Foundation (CHE-0203346). Bill Tolman is thanked for stimulating discussions and boundless enthusiasm.

Keywords

  • Copper peroxide
  • Copper superoxide
  • Density functional theory
  • Galactose oxidase
  • Raman spectroscopy

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