7313-97-5Relevant articles and documents
Deuterium-Hydrogen Exchange and Scrambling Reactions in the Pyrolysis of Labeled Cyclopentene. A Radical Mechanism
Kosnik, Kenneth G.,Benson, Sidney W.
, p. 2790 - 2795 (1983)
Inter- and intraradical mechanism that promote deuterium-hydrogen scrambling in labeled cyclopentene-d1 are investigated at 800 K and 1200 K.Rate constants are estimated for each step and for possible competing side reactions.The fast radical bimolecular exchange at 800 K and unimolecaular scrambling at 1200 K of labeled cyclopentene are shown to be faster than the Woodward-Hoffman allowed 1,4 concerted molecular elimination of hydrogen.The low-energy estimate of 8.0 kcal/mol by Lewis of the difference between the allowed 1,4 and disallowed 1,2 channels can thus be explained.No conclusions can be drawn concerning the 1,2 channel.The estimated rates of radical reactions are in agreement with experiments on the addition of D2 to cyclopentadiene at 300 deg C which shows only cis, 3-5 addition and with pyrolysis experiments at 500 +/- 20 deg C which show about 5percent contribution of a higher than first-order radical reaction.The mechanism of this radical decomposition is given and its steps are explicitly evaluated.
