受限制几何条件下电子转移反应的反应和重排自由能。

Reaction and reorganization free energies of electron-transfer reactions under restricted geometry conditions.

机构信息

The Department of Physical Chemistry, Faculty of Chemistry, University of Seville.

出版信息

J Phys Chem B. 2010 Jul 22;114(28):9094-100. doi: 10.1021/jp1013626.

PMID:20583775

Abstract

Electron-transfer reactions between iron and cobalt complexes were studied in beta-cyclodextrin (betaCD), 2-hydroxypropyl-beta-cyclodextrin (HbetaCD), and 18-crown-6 ether (18C6) solutions. The results were rationalized taking as the basis the Marcus-Hush formalism. We employed two different approaches, depending on the kind of receptor and solvent, to obtain the reorganization and reaction free energies that determine the reaction rate constant. The opposite trends in reactivity observed in betaCD and HbetaCD solutions and the behavior in solutions of 18C6 are explained.

摘要

在β-环糊精（β-CD）、2-羟丙基-β-环糊精（Hβ-CD）和 18-冠-6 醚（18C6）溶液中研究了铁和钴配合物之间的电子转移反应。根据马库斯-休斯形式主义，对结果进行了合理化解释。我们采用了两种不同的方法，根据受体和溶剂的种类，获得了决定反应速率常数的重组和反应自由能。解释了在β-CD 和 Hβ-CD 溶液中观察到的反应活性的相反趋势以及在 18C6 溶液中的行为。