title: Engineering reactions in crystalline solids: predicting photochemical decarbonylation from calculated thermochemical parameters.
abstract: A detailed thermochemical analysis of the alpha-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 alpha-cleavage and decarbonylation steps. An excellent correlation between calculated values and previous experimental observations suggests that photochemical alpha-cleavage and decarbonylation in crystals should be predictable from knowledge of excitation energies and the RSE of the substituent.
authors.affiliation: Department of Chemistry, California State University Dominguez Hills, Carson, CA 90747, USA.
authors.forename: Luis M
authors.initials: LM
authors.lastname: Campos
authors.forename: Hung
authors.initials: H
authors.lastname: Dang
authors.forename: Danny
authors.initials: D
authors.lastname: Ng
authors.forename: Zhe
authors.initials: Z
authors.lastname: Yang
authors.forename: Hernan L
authors.initials: HL
authors.lastname: Martinez
authors.forename: Miguel A
authors.initials: MA
authors.lastname: Garcia-Garibay
mesh_terms: D000096:Acetone / Q000737:chemistry; D003460:Crystallization; D004952:Esters / Q000737:chemistry; D007659:Ketones / Q000737:chemistry*; D008956:Models, Chemical; D008958:Models, Molecular; D010777:Photochemistry; D013816:Thermodynamics
chemical_list: D004952:Esters; D007659:Ketones; D000096:Acetone