New perspective of electron transfer chemistry
New perspective of electron transfer chemistry
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DOI：
10.1039/b300053b
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发表时间：
2003-02-21
影响因子：
3.2
通讯作者：
Fukuzumi, S
中科院分区：
文献类型：
--
作者：
Fukuzumi, S
为精细控制人工光合作用化合物电荷分离状态下的电子转移反应，包括反电子转移反应及其合成应用，介绍了电子转移化学的新视角。根据电子转移的马库斯理论，描述了有效电子转移系统中合适组分的基本电子转移性质，并将其应用于设计能够很好地模拟光合作用反应中心功能的多步电子转移系统。分子间和分子内的电子转移过程都受到电子转移过程中产生的自由基阴离子与充当Lewis酸的金属离子的络合作用的精细控制。根据金属离子对电子转移反应的促进作用，给出了测定各种金属离子Lewis酸度的定量方法。金属离子催化电子转移反应的机理是可行的，它是通过自由基阴离子与金属离子络合而实现的，它涉及到以金属离子促进的电子转移过程作为决定反应速率的步骤。
A new perspective of electron transfer chemistry is described for fine control of electron transfer reactions including back electron transfer in the charge separated state of artificial photosynthetic compounds and its synthetic application. Fundamental electron transfer properties of suitable components of efficient electron transfer systems are described in light of the Marcus theory of electron transfer, in particular focusing on the Marcus inverted region, and they are applied, to design multi-step electron transfer systems which can well mimic the function of a photosynthetic reaction center. Both intermolecular and intramolecular electron transfer processes are finely controlled by complexation of radical anions, produced in the electron transfer, with metal ions which act as Lewis acids. Quantitative measures to determine the Lewis acidity of a variety of metal ions are given in relation to the promoting effects of metal ions on the electron transfer reactions. The mechanistic viability of metal ion catalysis in electron transfer reactions is demonstrated by a variety of examples of chemical transformations involving metal ion-promoted electron transfer processes as the rate-determining steps, which are made possible by complexation of radical anions with metal ions.