THE Hg 6(3P1) PHOTOSENSITIZED DECOMPOSITION OF CYCLOHEXENE VAPOR

Abstract

The reaction follows the pattern established for the triplet state reactions of olefins in general. The major products, ethylene, 1,3-butadiene, vinylcyclobutane, cyclohexane, various C12-compounds, and polymer, can best be accounted for by the allylic C—H and C—C bond cleavage of the primary triplet biradicals and the ring closure and fragmentation reactions of the resulting open chain biradicals. At least three types of triplet state species must be involved in the mechanism. The rate equations, developed on the assumed mechanism, satisfactorily describe the observed product distribution and kinetic features of the system and permit the estimation of the elementary rate constant values and the lifetimes of the various transient biradicals involved. Preliminary experiments with cycloheptene indicate that vinylcyclopentane is an important product.