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
超氧
金属配合物L(H(2)O)MOO(2+)(L =(H(2)O)(4),(NH(3))(4)或N(4)-大环; M = Cr (III),Rh(III))根据
化学计量L(H(2)O)MOO(2+)+ 3I(-)+ 3H(+)-> L(H(2)O MOH(2+)+ 1.5I(2)+ H(2)O。速率定律是-d [L(H(2)O)MOO(2 +)] / dt = k [L(H(2)O)MOO(2 +)] [I(-)] [H(+ )],其中Cr(aq)OO(2+)的k = 93.7 M(-2)s(-1),([14] aneN(4))(H(2)O)CrOO(2+)的k = 93.7 M(-2)s(-1) )和(888(对于在酸性
水溶液中在25摄氏度和0.50 M离子强度下)的(NH(3))(4)(H(2)O)RhOO(2+)。Cr(aq)OO(2 +)/ I(-)反应表现出逆溶剂动力学同位素效应,k(H)()2(O)/