六钨酸四丁基铵盐和异丙醇体系的催化氧化反应的ESR研究Ⅱ.

ESR STUDY ON THE CATALYTIC OXIDATION IN SYSTEM OF TETRABUTYLAMMONIUM HEXATUNGSTATE AND ISOPROPYL ALCOHOL II.

前言 近年来,关于同多酸、杂多酸及其盐类的光催化研究报道较多,而用电解方法研究它们的催化反应则很少见报道。本文采用恒电位电解条件,将六钨酸四丁基铵中的钨(Ⅵ)还原成钨(Ⅴ),再考察其催化异丙醇的氧化反应。结果表明,[W_6O_(19)]^(2-)非但具有光化学活性,也具有电化学活性。我们用电子自旋共振和自旋捕捉相结合的方法,检测到反应过程中产生的自由基中间体。用计算机模拟方法确定其结构,因而对机理的讨论更为清楚。

Under electrolysis condition, the active radical media generated in system of tetrabutylammonium hexatungstate and isbpropyl alcohol were detected in situ, using spin-trapping with ESR technique. The chemical structure of some radicals was comfirmcd through computer simulation. The mechanism of the reaction was also discussed.