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Reaction of atomic oxygen with cyclopentadiene

✍ Scribed by Kazumoto Nakamura; Seiichiro Koda

Publisher
John Wiley and Sons
Year
1977
Tongue
English
Weight
662 KB
Volume
9
Category
Article
ISSN
0538-8066

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✦ Synopsis

The reaction of 1,3-cyclopentadiene (CPD) with ground-state atomic oxygen O ( 3 P ) , produced by mercury photosensitized decomposition of nitrous oxide, was studied. The identified products were carbon monoxide and the following C4H6 isomers: 3-methylcyclopropene, 1,3-butadiene, 1,2-butadiene, and 1-butyne. The yield of carbon monoxide over oxygen atoms produced ( 4 ~0 )

was equal to the sum of the yields of C4Ha isomers in any experiment.

We did not succeed in detecting any addition products such as CsHsO isomers. I t was found that 3-methylcyclopropene was produced with excess energy and was partly isomerized to other C& isomers, especially to 1-butyne. The excess energy was estimated to be about 50 kcal/mol. The rate coefficient of the reaction was obtained relative to those for the reactions of atomic oxygen with trans-2-butene and 1-butene. The ratios kCPD+O/klrons-2-butenef~ = 2.34 and kCPD+O/kl-butene+O = 11.3 were obtained. was 0.43 at the total pressure of 6.5 torr and 0.20 a t 500 torr.

Probable reaction mechanisms and intermediates are suggested.

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