Engineering Reactions in Crystalline Solids: Predicting Photochemical Decarbonylation from Calculated Thermochemical Parameters
- 26 April 2002
- journal article
- research article
- Published by American Chemical Society (ACS) in The Journal of Organic Chemistry
- Vol. 67 (11), 3749-3754
- https://doi.org/10.1021/jo016371v
Abstract
A detailed thermochemical analysis of the α-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 α-cleavage and decarbonylation steps. An excellent correlation between calculated values and previous experimental observations suggests that photochemical α-cleavage and decarbonylation in crystals should be predictable from knowledge of excitation energies and the RSE of the substituent.This publication has 13 references indexed in Scilit:
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