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 language | English (US) |
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Pages (from-to) | 10936-10940 |
Number of pages | 5 |
Journal | Angewandte Chemie - International Edition |
Volume | 58 |
Issue number | 32 |
DOIs | |
State | Published - Aug 5 2019 |
Keywords
- Raman spectroscopy
- bioinorganic chemistry
- copper
- nitrogen oxides
- peroxynitrite
ASJC Scopus subject areas
- Catalysis
- General Chemistry