Simultaneous capture of two distinct radical ion intermediates generated from the EDA complexes of three-membered compounds with TCNE by photoexcitation and in the dark

Journal Article · Wed Apr 29 00:00:00 EDT 1987 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00243a035· OSTI ID:6800210

Miyashi, T; Kamata, M; Mukai, T

Irradiation of the electron donor-acceptor (EDA) complexes of 2,2-diaryl-1-methylenecyclopropanes, 1,1,2,2-tetraarylcyclopropanes, 2,3-diaryloxiranes, or 2,3-diarylaziridines with tetracyanoethylene (TCNE) under aerated conditions involved oxygenation and/or the (3 + 2) cycloaddition with TCNE. The same oxygenation took place in the dark when the EDA complexes of 2,2-diaryl-1-methylenecyclopropanes or 1,1,2,2-tetraarylcyclopropanes with TCNE were simply stirred in oxygen-saturated solvents. Oxygenation occurred much more efficiently as the solvent polarity and the electron-donative nature of donor substrates increased. 1,2,4,5-Tetramethoxybenzene (TMB) used as a quencher efficiently suppressed oxygenation but not the (3 + 2) cycloaddition at all. Oxygenation occurs through the solvent-separated radical cations diffused from the photogenerated geminate radical ion pairs, whereas the cage coupling of the radical ion pairs involves the (3 + 2) cycloaddition with TCNE.

• Research Organization: Tohoku Univ., Sendai, Japan
• OSTI ID: 6800210
• Journal Information: J. Am. Chem. Soc.; (United States), Vol. 109:9
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ALKENES
PHOTOCHEMICAL REACTIONS
CYCLOALKANES
EPOXIDES
ORGANIC NITROGEN COMPOUNDS
PROPANE
CATIONS
DIFFUSION
ELECTRON TRANSFER
EXPERIMENTAL DATA
OXYGEN
PHOTOCHEMISTRY
RADICALS
REACTION INTERMEDIATES
SOLVENT PROPERTIES
ALKANES
CHARGED PARTICLES
CHEMICAL REACTIONS
CHEMISTRY
DATA
ELEMENTS
HYDROCARBONS
INFORMATION
IONS
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
400500* - Photochemistry