Abstract
We report the formation of a new copper peroxynitrite (PN) complex [Cu(II) (TMG(3) tren)(κ(1) -OONO)](+) (PN1) from the reaction of [Cu(II) (TMG(3) tren)(O(2)(.-) )](+) (1) with NO(.)((g)) at -125 °C. The first resonance Raman spectroscopic characterization of such a metal-bound PN moiety supports a cis κ(1) -((-) OONO) geometry. PN1 transforms thermally into an isomeric form (PN2) with κ(2) -O,O'-((-) OONO) coordination, which undergoes O-O bond homolysis to generate a putative cupryl (LCu(II) -O(.) ) intermediate and NO(2)(.) . These transient species do not recombine to give a nitrato (NO(3)(-) ) product but instead proceed to effect oxidative chemistry and formation of a Cu(II) -nitrito (NO(2)(-) ) complex (2).