Acid-catalyzed oxidation of iodide ions by superoxo complexes of rhodium and chromium

Superoxometal complexes L(H(2)O)MOO(2+) (L = (H(2)O)(4), (NH(3))(4), or N(4)-macrocycle; M = Cr(III), Rh(III)) react with iodide ions according to the stoichiometry L(H(2)O)MOO(2+) + 3I(-) + 3H(+) --> L(H(2)O)MOH(2+) + 1.5I(2) + H(2)O. The rate law is -d[L(H(2)O)MOO(2+)]/dt = k [L(H(2)O)MOO(2+)][I(-)][H(+)], where k = 93.7 M(-2) s(-1) for Cr(aq)OO(2+), 402 for ([14]aneN(4))(H(2)O)CrOO(2+), and 888 for (NH(3))(4)(H(2)O)RhOO(2+) in acidic aqueous solutions at 25 degrees C and 0.50 M ionic strength. The Cr(aq)OO(2+)/I(-) reaction exhibits an inverse solvent kinetic isotope effect, k(H)()2(O)/k(D)2(O) = 0.5. In the proposed mechanism, the protonation of the superoxo complex precedes the reaction with iodide. The related Cr(aq)OOH(2+)/I(-) reaction has k(H)2(O)/k(D)2(O) = 0.6. The oxidation of (NH(3))(5)Rupy(2+) by Cr(aq)OO(2+) exhibits an [H(+)]-dependent pathway, rate = (7.0 x 10(4) + 1.78 x 10(5)[H(+)])[Ru(NH(3))(5)py(2+)][Cr(aq)OO(2+)]. Diiodine radical anions, I(2)(*)(-), reduce Cr(aq)OO(2+) with a rate constant k = 1.7 x 10(9) M(-1) s(-1).