Effects of Free Energy and Solvent on Rates of Intramolecular Electron Transfer in Organic Radical Anions

2017 ◽  
Vol 121 (38) ◽  
pp. 7297-7306 ◽  
Author(s):  
William W. Parson
Keyword(s):  
Electron Transfer ◽  
Free Energy ◽  
Organic Radical ◽  
Intramolecular Electron Transfer ◽  
Radical Anions

Paramagnetic organometallic molecules. XIV. Ion-pair and steric effects in dissociative electron transfer reactions of metal cluster carbonyl radical anions

1983 ◽  
Vol 36 (3) ◽  
pp. 441 ◽  
Author(s):  
CM Kirk ◽  
BM Peake ◽  
BH Robinson ◽  
J Simpson
Keyword(s):  
Electron Transfer ◽  
Metal Cluster ◽  
Metal Carbonyl ◽  
Electron Attachment ◽  
Transfer Reactions ◽  
Organic Radical ◽  
Radical Anions ◽  
Dissociative Electron Attachment ◽  
Dissociative Electron Transfer ◽  
Electron Transfer Reactions

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.

Intramolecular electron transfer and SN2 reactions in the radical anions of 1-(4-biphenylyl)-.omega.-haloalkane studied by pulse radiolysis

1981 ◽  
Vol 103 (17) ◽  
pp. 5176-5179 ◽  
Author(s):  
Hitoshi Kigawa ◽  
Setsuo Takamuku ◽  
Susumu Toki ◽  
Norio Kimura ◽  
Seishi Takeda ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Pulse Radiolysis ◽  
Intramolecular Electron Transfer ◽  
Radical Anions ◽  
Sn2 Reactions

scholarly journals Catalytic control of electron-transfer processes

2003 ◽  
Vol 75 (5) ◽  
pp. 577-587 ◽  
Author(s):  
Shunichi Fukuzumi
Keyword(s):  
Electron Transfer ◽  
Metal Ions ◽  
Metal Ion ◽  
Photochemical Reactions ◽  
Transfer Reactions ◽  
Intramolecular Electron Transfer ◽  
Radical Anions ◽  
Electron Transfer Reactions ◽  
Transfer Processes ◽  
Electron Transfer Processes

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.

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