Evidence for a chair cyclohexane-1,4-radical cation intermediate in the single electron-transfer-induced Cope rearrangement of 2,5-diaryl-1,5-hexadienes

1988 ◽  
Vol 110 (11) ◽  
pp. 3676-3677 ◽  
Author(s):  
Tsutomu. Miyashi ◽  
Akinori. Konno ◽  
Yasutake. Takahashi
Keyword(s):  
Electron Transfer ◽  
Radical Cation ◽  
Single Electron ◽  
Cope Rearrangement ◽  
Single Electron Transfer

The oxidation of sulfides by chromium(V)

2003 ◽  
Vol 81 (1) ◽  
pp. 75-80 ◽  
Author(s):  
Carmela R Jackson Lepage ◽  
Lynn Mihichuk ◽  
Donald G Lee
Keyword(s):  
Electron Transfer ◽  
Molecular Orbital ◽  
Radical Cation ◽  
Oxygen Transfer ◽  
Single Electron ◽  
Frontier Molecular Orbital ◽  
Molecular Orbital Calculations ◽  
Single Electron Transfer ◽  
Oxidation Of Sulfides

The mechanism for the oxidation of sulfides by [(me4-salen)CrV(O)(pyO)]CF3SO3, where me4-salen is 8,8,8',8'-tetramethylsalen and pyO is pyridine N-oxide, has been investigated. Results from Hammett correlations on the rates of oxidation of substituted thioanisoles, frontier molecular orbital calculations, and product studies are consistent with a mechanism that is initiated by a single electron transfer to give a radical cation intermediate.Key words: oxidation, chromium(V), sulfides, radical cation, oxygen transfer.

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