van Gorkum Remy, Bouwman Elisabeth, Reedijk Jan
Leiden Institute of Chemistry, Leiden University, P.O. Box 9502, 2300 RA Leiden, The Netherlands.
Inorg Chem. 2004 Apr 19;43(8):2456-8. doi: 10.1021/ic0354217.
It has been found that [Mn(acac)(3)], by functioning both as a radical initiator and a hydroperoxide decomposition catalyst, has a very high activity in the autoxidation of ethyl linoleate (EL), a model compound for the binder molecule in household alkyd paint. Adding 1 equiv of bipyridine (bpy) to a reaction mixture of EL and [Mn(acac)(3)] significantly enhances the autoxidation rate. The redox properties of [Mn(acac)(3)] and [Mn(acac)(2)(bpy)] have been compared with cyclic voltammetry; the observed peak potentials show that addition of bpy facilitates reduction of Mn(III) to Mn(II), which may explain the increase in autoxidation activity.
已发现，[Mn(acac)(3)]既作为自由基引发剂又作为氢过氧化物分解催化剂，在家用醇酸漆中粘合剂分子的模型化合物亚油酸乙酯（EL）的自氧化反应中具有非常高的活性。向EL和[Mn(acac)(3)]的反应混合物中加入1当量的联吡啶（bpy）可显著提高自氧化速率。已通过循环伏安法比较了[Mn(acac)(3)]和[Mn(acac)(2)(bpy)]的氧化还原性质；观察到的峰值电位表明，加入bpy有助于将Mn(III)还原为Mn(II)，这可能解释了自氧化活性的增加。
