A Peroxynitrite Dicopper Complex: Formation via Cu-NO and Cu-O₂ Intermediates and Reactivity via O-O Cleavage Chemistry.

ABSTRACT: A mixed-valent Cu(I)Cu(II) complex, [Cu^I,II₂(UN-O^-)]²⁺ (1), reacts with NO_(g) at -80 °C to form [Cu^I,II₂(UN-O^-)(NO)]²⁺ (2), best described as a mixed-valent nitrosyl complex that has a ν(N-O) band at 1670 cm^-1 in its infrared (IR) spectrum. Complex 2 undertakes a one-electron oxidation via the addition of O_2(g) to generate a new intermediate, best described as a superoxide and nitrosyl adduct, [Cu^II₂(UN-O^-)(NO)(O₂^-)]²⁺ (3), based on its distinctively blue-shifted ν(N-O) band at 1853 cm^-1. Over the course of 20 min at -80 °C, 3 is converted to the peroxynitrite (PN) complex [Cu^II₂

SUBMITTER: Cao R 

PROVIDER: S-EPMC5293595 | biostudies-literature | 2016 Dec

REPOSITORIES: biostudies-literature