Using inherent radical stabilization energies to predict unknown enthalpies of formation and associated bond dissociation energies of complex molecules

Many free radical reactions are used currently for syntheses not easily accomplished by other methods. Hence, there is an increasing need for information about bond dissociation energies and enthalpies of formation of the molecules and radicals than is currently available for the more complex species involved in such reactions. We provide 98 standard enthalpies of formation that are not available in the extensive NIST database (number 69), 127 bond dissociation energies not experimentally available, and many previously unknown or uncertain enthalpies of formation of radicals, all at 298 K. A method is presented that allows one to obtain good predictions of the thermodynamic properties of new species using the inherent radical stabilities of their components. The information should be useful for designing and rationalizing synthetic radical reactions. (C) 2016 Elsevier Ltd. All rights reserved.