Photochemical Doping of TCNQ by Photoinduced Electron Transfer and C-C Cleavage of Radical Cation

1999 ◽  
Vol 28 (3) ◽  
pp. 241-242 ◽  
Author(s):  
Hajime Yokoi ◽  
Katsuya Ishiguro ◽  
Yasuhiko Sawaki
Keyword(s):  
Electron Transfer ◽  
Radical Cation ◽  
Photoinduced Electron Transfer

Products from photochemical reactions and electrochemical oxidation of methylenecyclopropane

1997 ◽  
Vol 75 (12) ◽  
pp. 1795-1809 ◽  
Author(s):  
H.J.P. de Lijser ◽  
T. Stanley Cameron ◽  
Donald R. Arnold
Keyword(s):  
Electron Transfer ◽  
Ionization Potential ◽  
Radical Cation ◽  
Photoinduced Electron Transfer ◽  
Nucleophilic Addition ◽  
Major Product ◽  
Oxidation Potential ◽  
Photochemical Reactions ◽  
Tert Butyl ◽  
Adiabatic Ionization Potential

The reactivity of methylenecyclopropane (MCP, 1) and its radical cation (1+•) have been studied in the presence and absence of a nucleophile (methanol). Photochemical reactions of 1 in the presence of an electron-acceptor (1,4-dicyanobenzene, 6) and a codonor (biphenyl, 7) in acetonitrile (with and without methanol present) or chloroform lead to cycloadditions (ortho, meta, and para; products 12–17) rather than products from photoinduced electron transfer (PET). Based on the measured (cyclic voltammetry, CV) oxidation potential, using the Weller equation, electron transfer (ET) was predicted to occur. It was shown that the measured oxidation potential of 1 represents the adiabatic ionization potential. For PET processes the value for the vertical ionization potential must be used. Electrochemical (EC) generation of 1+• without a nucleophile present results in the formation of one major product: tert-butyl acetamide (25). A series of rearrangements leading to the tert-butyl cation is proposed. Addition of a nucleophile (methanol) to the mixture leads to the formation of 3-methoxy-2-(methoxymethyl)-1-propene (26). This product may arise from trapping of the initially formed ring-opened (trimethylenemethane) radical cation (1a+•), which undergoes a second oxidation and nucleophilic addition (ECE). Keywords: methylenecyclopropane, radical cation, photochemistry, electrochemistry, photocycloaddition.

scholarly journals Radical Cation Cycloaddition Reactions of 2-Vinylbenzofurans and 2-Vinylfurans by Photoinduced Electron Transfer.

1998 ◽  
Vol 52 ◽  
pp. 175-193 ◽  
Author(s):  
Jörg Botzem ◽  
Udo Haberl ◽  
Eberhard Steckhan ◽  
Siegfried Blechert ◽  
Inger Søtofte ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Radical Cation ◽  
Photoinduced Electron Transfer ◽  
Cycloaddition Reactions
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