Genre
- Journal Article
The thermal decomposition of phenylehlorodiazirine (1), phenyl-n-butyldiazirine (2), and 2-adamantane-2,3'-[3H] diazirine (3) has been studied in solution in the presence Of C-60. The C-60 probe technique indicates that in the decomposition diazirine 1 yielded exclusively phenylchlorocarbene, diazirine 2 yielded mainly a diazo intermediate, and diazirine 3 yielded a mixture of carbene and diazo compound. In the case of diazirine 2, 13% of (E)-1-phenyl-1-pentene resulted from the direct thermal rearrangement of diazirine without the participation of a carbene. As well, the thermal decomposition of these diazirines has been studied theoretically with ab initio and density functional methods. The experimental results are broadly in agreement with the theoretical predictions. The calculations further indicate that the rebound reaction between carbene and molecular nitrogen leading to the formation of a diazo intermediate is an important reaction in the gas-phase decomposition of diazirine.
Univ Prince Edward Isl, Dept Chem, Charlottetown, PE C1A 4P3, Canada. Inst Mol Sci, Dept Theoret Studies, Okazaki, Aichi 4448585, Japan. Univ Tsukuba, Ctr Tsukuba Adv Res Alliance, Tsukuba, Ibaraki 3058577, Japan. Niigata Univ, Grad Sch Sci & Te(TRUNCATED)
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AMER CHEMICAL SOC
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Source type: Electronic(1)
Language
- English
Subjects
- energy
- MIGRATION
- MECHANISM
- DIAZOMETHANE
- Chemistry, Organic
- PERTURBATION-THEORY
- METHYLENE
- Density
- FULLERENES
- photolysis
- EXCITED-STATES