ESR study of the aziridine and azetidine radical cations: evidence for the C. C ring-opened aziridine radical cation

Journal Article · Thu May 22 04:00:00 EDT 1986 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100402a005· OSTI ID:5497188

Qin, X Z; Williams, F

The radical cations from aziridine and azetidine have been characterized by ESR spectroscopy following their generation in the solid state by ..gamma.. irradiation of dilute solutions of the parent compounds in the CFCl/sub 3/ matrix at 77 K. The ESR parameters of the azetidine radical cation are typical of those for nitrogen-centered amine radical cations such as Me/sub 2/NH*/sup +/. On the other hand, the radical cation formed from aziridine has very different ESR parameters that compare closely to those for the isoelectronic C...C ring-opened form of the oxirane radical cation and the allyl radical. The radical cation formed from azetidine is therefore assigned a ring-closed structure with the unpaired electron in a 2p/sub z/ orbital on nitrogen perpendicular to the ring plane, whereas the cation from aziridine is an allylic C...C ring-opened planar isomer with the unpaired electron in a nonbonding ..pi.. orbital centered mainly on the two end carbon atoms. The neutral 1-aziridinyl and 1-azetidinyl radicals have been detected as radical products following the ..gamma.. irradiation of the parent compounds in the CFCl/sub 2/CF/sub 2/Cl and CF/sub 3/CCl/sub 3/ matrices. In particular, the 1-azetidinyl radical is produced cleanly from the azetidine radical cation in the CFCl/sub 2/CF/sub 2/Cl matrix at ca. 100 K.

• Research Organization: Univ. of Tennessee, Knoxville
• OSTI ID: 5497188
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 90:11; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
400600 -- Radiation Chemistry
AZIDO COMPOUNDS
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTIONS
CHEMISTRY
DATA
DECOMPOSITION
DEUTERIUM COMPOUNDS
ELECTROMAGNETIC RADIATION
ELECTRON SPIN RESONANCE
EXPERIMENTAL DATA
GAMMA RADIATION
HYDROGEN COMPOUNDS
INFORMATION
IONIZING RADIATIONS
MAGNETIC RESONANCE
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
RADIATION CHEMISTRY
RADIATION EFFECTS
RADIATIONS
RADICALS
RADIOLYSIS
REACTION INTERMEDIATES
RESONANCE