Catalytic control of electron-transfer processes
S. Fukuzumi
Department of Material and Life Science, Graduate
School of Engineering,
Osaka University, Crest, Japan Science and Technology Corporation,
2-1 Yamada-oka, Suita, Osaka 565-0871, Japan
Abstract: Catalytic control of electron-transfer processes
is described for a number of photoinduced and thermal electron-transfer
reactions, including back electron transfer in the charge-separated
state of artificial photosynthetic compounds. The intermolecular and
intramolecular electron-transfer processes are accelerated by complexation
of radical anions, produced in the electron transfer, with metal ions
that act as Lewis acids. Quantitative measures to determine the Lewis
acidity of a variety of metal ions are given in relation with the promoting
effects of metal ions in the electron-transfer reactions. The mechanistic
viability of metal ion catalysis in electron-transfer reactions is demonstrated
by a variety of examples of both thermal and photochemical reactions
that involve metal ion-promoted electron-transfer processes as the rate-determining
steps, which are made possible to proceed by complexation of radical
anions with metal ions.
*Plenary lectures presented at the 16th International Conference on Physical Organic Chemistry (ICPOC-16): Structure and Mechanism in Organic Chemistry,San Diego, California, USA, 4�9 August 2002. Other presentations are published in this issue, pp. 541�630.
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