Theoretical study on haloaromatic radical anions and their intramolecular electron transfer reactions

Author(s):  
Adriana B. Pierini ◽  
Jos� S. Duca
2003 ◽  
Vol 75 (5) ◽  
pp. 577-587 ◽  
Author(s):  
Shunichi Fukuzumi

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.


Author(s):  
Yoshiaki Furukawa ◽  
Yoichi Sugiyama ◽  
Satoshi Takahashi ◽  
Koichiro Ishimori ◽  
Isao Morishima

1983 ◽  
Vol 36 (3) ◽  
pp. 441 ◽  
Author(s):  
CM Kirk ◽  
BM Peake ◽  
BH Robinson ◽  
J Simpson

An investigation of electron attachment reactions of cluster metal carbonyls is presented. In general, alkyl and organometallic halides react rapidly with metal carbonyl cluster radical anions at ambient temperatures to give the neutral cluster molecule. Halide ion and alkyl or organometallic radicals are also produced, which indicate that these are dissociative electron attachment reactions analogous to those of organic radical anions. The rate of dissociative electron attachment in reactions of PhCCo3(CO)9- was found to depend on the R-X bond energy, the size of the alkyl group and the nature of the counter-ion. In particular, (Ph3P)2N+ retarded some electron transfer reactions to the extent that the bimolecular decay of PhCCo3(CO)9- effectively competed with the electron transfer process in determining the reaction path.


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