Reactions of a chromium(III)-superoxo complex and nitric oxide that lead to the formation of chromium(IV)-oxo and chromium(III)-nitrito complexes.
The reaction of an end-on Cr(III)-superoxo complex bearing a 14-membered tetraazamacrocyclic TMC ligand, [Cr(III)(14-TMC)(O2)(Cl)](+), with nitric oxide (NO) resulted in the generation of a stable Cr(IV)-oxo species, [Cr(IV)(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, [Cr(III)(14-TMC)(NO2)(Cl)](+). The Cr(IV)-oxo and Cr(III)-nitrito complexes were also characterized spectroscopically and/or structurally.
Department of Bioinspired Science and Department of Chemistry and Nano Science, Ewha Womans University , Seoul 120-750, Korea.
Atsutoshi
A
Yokoyama
Kyung-Bin
KB
Cho
Kenneth D
KD
Karlin
Wonwoo
W
Nam
D002857:Chromium / Q000737:chemistry*; D009569:Nitric Oxide / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry*
D009942:Organometallic Compounds; D002857:Chromium; D009569:Nitric Oxide; D010100:Oxygen