La photochimie du cis-penta-1,3-diène, en phase gazeuse à 184,9 et 147,0 nm

Abstract

We have studied the 184.9 and 147.0 nm photochemistry of gaseous cw-1,3-pentadiene: the main products observed at 184.9 nm are trans-1,3-pentadiene and 1,3-cyclopentadiene. The formation of radicals also occurs as shown through the use of DI as a radical scavenger. Cyclopentadiene is the likely product of successive eliminations of two hydrogen atoms from the photoexcited molecule after rearrangement of the pentadienyl radical to the cyclopentenyl structure: Ф0(cyclo-C5H6) ≈ 0.25. Elimination of a methyl radical (Ф0 ≈ 0.50) also occurs, with formation of CH2=CHCH=ĊH* and, in a lower yield, CH2=C=CHĊH2*. However, it is not possible to identify properly the mechanism of the formation of the latter radical. It may be the result of the isomerization of either the first photoexcited molecule or the excited 1,3-butadienyl radicals. A small amount of 1,4-pentadiene formation is also observed (Ф0 ≈ 0.035 ± 0.015). At 147.0 nm, the same characteristics are observed, together with higher fragmentation due to the higher energy content of the photoexcited molecules. It appears that the photofragmentation at both wavelengths is more in line with that of acyclic alkenes than with that of 1,3-butadiene, which tends to undergo isomerization of the photoexcited molecules to the 1,2-butadiene structure. Key words: 1,3-pentadiene, far UV, vacuum UV, photolysis, monomolecular, fragmentation, stabilization.