Davies Trevor J, Garner A Christopher, Davies Stephen G, Compton Richard G
Physical and Theoretical Chemistry Laboratory, Oxford University, South Parks Road, Oxford, OX1 3QZ, UK.
Chemphyschem. 2005 Dec 9;6(12):2633-9. doi: 10.1002/cphc.200500372.
Electrocatalytic processes can take place either homogeneously in a single liquid phase or heterogeneously at the liquid-liquid interface formed in emulsions. This Article addresses the question as to whether a change in rate and/or mechanism can occur between the two possibilities. Specifically, cyclic voltammetry and electrosynthetic experiments are used to demonstrate that for the vitamin B12 mediated reduction of vicinal dibromides producing olefins, electric field effects likely operate at the liquid-liquid interface which can change the populations of different conformers relative to the single homogeneous-phase experiment, leading to significant changes in rate.
电催化过程既可以在单一液相中均相地发生，也可以在乳液中形成的液 - 液界面处非均相地发生。本文探讨了在这两种可能性之间是否会发生速率和/或机理的变化这一问题。具体而言，循环伏安法和电合成实验被用于证明，对于维生素B12介导的邻二溴化物还原生成烯烃的反应，电场效应可能在液 - 液界面起作用，这相对于单一均相实验可能会改变不同构象体的数量，从而导致速率发生显著变化。
