Arene-iminium salt electron-transfer photochemistry. Mechanistically interesting photoaddition processes

Journal Article · Wed Apr 29 04:00:00 EDT 1987 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00243a028· OSTI ID:6629466

Borg, R M; Heuckeroth, R O; Lan, A J.Y.; Quillen, S L; Mariano, P S

Studies of the electron-transfer photochemistry of arene-iminium salt systems have been explored. Fluorescence quenching investigations have demonstrated that a series of arenes including substituted toluenes and benzenes quench the fluorescence of a variety of 2-aryl-1-pyrrolinium perchlorates. Quenching rate constants in these cases correlate with the ..delta..G/sub SET/ values as expected for quenching by reversible electron-transfer pathways. In addition, nonconjugated iminium salts quench the fluorescence of a host of arenes with k/sub q/ values which parallel those predicted on the basis of electron-transfer free energy calculations. Photoaddition reactions of toluene, benzyltrimethylsilane, benzyltrimethylstannane, and 2-aryl-1-pyrrolinium salts have been explored. Likewise, electron-transfer-induced, excited-state reactions of toluene and benzyltrimethylsilane with 1,2-dimethyl-1-pyrrolinium perchlorate have been investigated. The results of these photoreactions have been interpreted in terms of steric, electrofugal group, and solvent effects upon the rates of competitive pathways available to initially formed radical cation pair intermediates. Finally, the photochemistry of benzyltrimethylstannane is described.

• Research Organization: Univ. of Maryland, College Park
• OSTI ID: 6629466
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 109:9; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500* -- Photochemistry
AROMATICS
CATIONS
CHARGED PARTICLES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHEMISTRY
DATA
DE-EXCITATION
ELECTRON TRANSFER
ENERGY LEVELS
ENERGY TRANSFER
ENERGY-LEVEL TRANSITIONS
EXCITED STATES
EXPERIMENTAL DATA
IMINES
INFORMATION
IONS
KINETICS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOCHEMISTRY
RADIATIONLESS DECAY
RADICALS
REACTION INTERMEDIATES
REACTION KINETICS
SALTS
SOLVENT PROPERTIES
STEREOCHEMISTRY
THERMODYNAMICS