In aqueous perchloric acid medium (pH = 0.522 – 1.3), N–benzylhydroxylamine (two electron reductant) reduces the one electron oxidant, superoxo ligand in [(dien)(en)CoIII(O2)CoIII(en)(dien)](ClO4)5 (1) to the corresponding hydroperoxo complex,[(en)(dien)CoIII(HO2)CoIII(en)(dien)]5+ (2) and itself gets oxidised to PhCH2NO following both proton coupled electron transferpath and an electron transfer reaction. The kinetics, stoichiometry and reaction mechanism clearly indicate that oxidation of PhCH2NHOH occurs through the formation of an intermediate, benzyl derivative of aminoxyl radical (PhCH2NHO•). In thepresence of excess PhCH2NHOH over 1, the reaction obeys first-order kinetics and rate of the reaction increases with [PhCH2NHOH]. The reaction rate, however, decreases with increase in [H+] and the plot of 1/ko with [H+] is linear with a smallbut noteworthy intercept. It is also remarked that the reaction rate remarkably decreases with increasing proportion of D2O replacing H2O in the solvent. Therefore, an H-atom transfer from PhCH2NHOH to the bridging superoxide in 1 seems reasonable at the rate determining step

中文翻译：

---

高氯酸介质中 CoIII 结合的桥连超氧配合物氧化 N-苄基羟胺的动力学和机理研究

在水性高氯酸介质（pH = 0.522 – 1.3）中，N-苄基羟胺（双电子还原剂）还原 [(dien)(en)CoIII(O2)CoIII(en)(dien)]( ClO4)5 (1) 到相应的氢过氧化络合物，[(en)(dien)CoIII(HO2)CoIII(en)(dien)]5+ (2) 并且在质子耦合电子转移路径和电子转移反应。动力学、化学计量学和反应机理清楚地表明，PhCH2NHOH 的氧化是通过形成中间体、氨基氧自由基的苄基衍生物 (PhCH2NHO•) 发生的。在存在超过 1 的过量 PhCH2NHOH 时，反应服从一级动力学并且反应速率随着 [PhCH2NHOH] 的增加而增加。然而，反应速率 随着 [H+] 的增加而减小，并且 1/ko 与 [H+] 的图是线性的，截距很小但值得注意。还注意到，随着溶剂中 D2O 取代 H2O 的比例增加，反应速率显着降低。因此，在速率确定步骤中，H 原子从 PhCH2NHOH 转移到 1 中的桥接超氧化物似乎是合理的