Abstract
Previous work has found an electrophilic trend for the relative reactivities of C2O(X3Σ) with various olefins [1]. However, Trotman-Dickenson and coworkers found just the opposite trend, and concluded that C2O was a nucleophile in both its ground triplet and excited singlet states [2]. The present work was undertaken to resolve this disagreement. Direct competition between ethylene and a second olefin for C2C(X3Σ), which was formed by the photolysis of C3O2 at 3000 A, confirmed the previous electrophilic trend. The singlet state C2O, formed by photolysis at 2540 A, showed no strong selectivity among the olefins, again in disagreement with the previous work [2]. The relative reactivities of C2O(X3Σ) have been studied as a function of temperature. The activation energy decreases by about 4 kcal/mol in going from ethylene to tetramethyl ethylene, while the preexponential factor decreases by approximately a factor of ten. At room temperature, the activation energy effect dominates, and as a result tetramethyl ethylene is more reactive than ethylene. This behavior will be compared to that of other electrophilic reactants.
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