Reactions of a chromium(III)-superoxo complex and nitric oxide that lead to the formation of chromium(IV)-oxo and chromium(III)-nitrito complexes

Atsutoshi Yokoyama, Kyung Bin Cho, Kenneth D. Karlin, Wonwoo Nam

Research output: Contribution to journalArticlepeer-review

38 Scopus citations

Abstract

The reaction of an end-on Cr(III)-superoxo complex bearing a 14-membered tetraazamacrocyclic TMC ligand, [CrIII(14-TMC)(O2)(Cl)] +, with nitric oxide (NO) resulted in the generation of a stable Cr(IV)-oxo species, [CrIV(14-TMC)(O)(Cl)]+, via the formation of a Cr(III)-peroxynitrite intermediate and homolytic O-O bond cleavage of the peroxynitrite ligand. Evidence for the latter comes from electron paramagnetic resonance spectroscopy, computational chemistry and the observation of phenol nitration chemistry. The Cr(IV)-oxo complex does not react with nitrogen dioxide (NO2), but reacts with NO to afford a Cr(III)-nitrito complex, [CrIII(14-TMC)(NO2)(Cl)] +. The Cr(IV)-oxo and Cr(III)-nitrito complexes were also characterized spectroscopically and/or structurally.

Original languageEnglish
Pages (from-to)14900-14903
Number of pages4
JournalJournal of the American Chemical Society
Volume135
Issue number40
DOIs
StatePublished - 9 Oct 2013

Fingerprint

Dive into the research topics of 'Reactions of a chromium(III)-superoxo complex and nitric oxide that lead to the formation of chromium(IV)-oxo and chromium(III)-nitrito complexes'. Together they form a unique fingerprint.

Cite this