Web Release Date: April 26,
Engineering Reactions in Crystalline Solids: Predicting Photochemical Decarbonylation from Calculated Thermochemical Parameters
and
Department of Chemistry, California State University Dominguez Hills, Carson, California 90747, and Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095-1569
Received December 13, 2001
Abstract:
A detailed thermochemical analysis of the 
-cleavage and decarbonylation reactions of acetone
and several ketodiesters was carried out with the B3LYP/6-31G* density functional method. The
heats of formation of several ground-state ketones and radicals were calculated at 298 K to determine
bond dissociation energies (BDE) and radical stabilization energies (RSE) as a function of
substituents. Results show that the radical-stabilizing abilities of the ketone substituents play a
very important role on the thermodynamics of the -cleavage and decarbonylation steps. An excellent
correlation between calculated values and previous experimental observations suggests that
photochemical -cleavage and decarbonylation in crystals should be predictable from knowledge
of excitation energies and the RSE of the substituent.
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