Abstract

The role of photocatalysts in improving the photochemical synthesis of fatty amines has been examined. Ab initio SCF and CI calculations for the addition of the aminyl radical NH 2 • to ethylene are reported. In contrast with previous theoretical results a low activation energy and a rather small exothermicity were determined. Thus an explanation for the known inactivity of amino radicals in addition reactions can be found in the possibility of a retroaddition. The calculations indicate that the role of photocatalysts could be explained by a significant stabilization of the addition photoproduct blocking the reversibility of the process. The involvement of the photocatalyst with the primary photoproduct NH 2 • should also be considered in view of a significant increase in the exothermicity observed.

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