Direct Resonance Raman Characterization of a Peroxynitrito Copper Complex Generated from O2 and NO and Mechanistic Insights into Metal-Mediated Peroxynitrite Decomposition

Jeffrey J. Liu, Maxime A. Siegler, Kenneth D. Karlin, Pierre Moenne-Loccoz

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Abstract

We report the formation of a new copper peroxynitrite (PN) complex [CuII(TMG3tren)(κ1-OONO)]+ (PN1) from the reaction of [CuII(TMG3tren)(O2.−)]+ (1) with NO.(g) at −125 °C. The first resonance Raman spectroscopic characterization of such a metal-bound PN moiety supports a cis κ1-(OONO) geometry. PN1 transforms thermally into an isomeric form (PN2) with κ2-O,O′-(OONO) coordination, which undergoes O−O bond homolysis to generate a putative cupryl (LCuII−O.) intermediate and NO2.. These transient species do not recombine to give a nitrato (NO3) product but instead proceed to effect oxidative chemistry and formation of a CuII–nitrito (NO2) complex (2).

Original languageEnglish (US)
JournalAngewandte Chemie - International Edition
DOIs
StatePublished - Jan 1 2019

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Keywords

  • bioinorganic chemistry
  • copper
  • nitrogen oxides
  • peroxynitrite
  • Raman spectroscopy

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

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