Electron spin resonance evidence for the 1,4-bishomobenzene structure of the C sub 2. nu. ring-opened semibullvalene (bicyclo(3. 3. 0)octa-2,6-diene-4,8-diyl) radical cation

Journal Article · Tue Mar 27 23:00:00 EST 1990 · Journal of the American Chemical Society; (USA)

DOI:https://doi.org/10.1021/ja00163a074· OSTI ID:6518908

Dai, Sheng; Wang, Jih Tzong; Williams, F ^[1]

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1. Univ. of Tennessee, Knoxville (USA)

The remarkable fact that semibullvalene (1) undergoes a rapid degenerate Cope rearrangement on the NMR time scale at {minus}150{degree}C has prompted efforts to lower the activation energy of only 4.8 kcal mol{sup {minus}1} for the parent molecule to a negative value by appropriate substitution. This exciting goal where the expected 1,4-bishomobenzene transition structure would be stabilized relative to the localized semibullvalene structures has not hitherto been realized, however, even for purposely designed derivatives. In contrast, they now report that radiolytic oxidation of 1 in Freon matrices generates the delocalized bicyclo(3.3.0)octa-2,6-diene-4,8-diyl radical cation 2{sup {sm bullet}+} as a stable species.

• DOE Contract Number: FG05-88ER13852
• OSTI ID: 6518908
• Journal Information: Journal of the American Chemical Society; (USA), Journal Name: Journal of the American Chemical Society; (USA) Vol. 112:7; ISSN 0002-7863; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
CATIONS
CHARGED PARTICLES
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTIONS
CHEMISTRY
DATA
DATA ANALYSIS
DECOMPOSITION
ELECTRON SPIN RESONANCE
EXPERIMENTAL DATA
INFORMATION
IONS
MAGNETIC RESONANCE
MEASURING METHODS
NUMERICAL DATA
ORGANIC COMPOUNDS
OXIDATION
RADIATION CHEMISTRY
RADIATION EFFECTS
RADIOLYSIS
RESONANCE