In the framework of our theoretical approach of the structure and reactivity of chemical intermediates we have been led to reexamine the concept of stability which is widely used by the experimentalists often without specifying its true meaning. In this work we propose a more general definition of the concept of stabilization energy, namely, where AHa is the heat of atomization of the species under consideration and the E A~' s are standard bond energy terms derived from the heats of atomization of reference compounds. Using experimental heats of formation or semiempirical ones deduced from theoretical heats of reaction of appropriate isodesmic processes, we have calculated the stabilization energies or various types of chemical species: saturated, unsaturated and conjugated molecules, free radicals, carbocations, and carbanions. The results obtained can be rationalized in terms of steric hindrance, angular strain, polar interactions, clectron delocalization, and substituent effects. Moreover, we have shown that heats of hydrogenation and bond dissociation energies do not provide accurate information on the thermodynamic stabilization of unsaturated compounds and free radicals, respectively. Among other applications the concept of stabilization energy allowed us to propose a detailed classification of free radicals and to rationalize their reactivity. Considering the particular case of radical recombination reactions we have been able : J deduce interesting equations showing the relations between the concept of stabilization energy and other quantities commonly used in chemical physics, namely, the bond cleavage enthalpy [BDE(C-C) if one considers alkane thermolysis], the thermodynamic stability measured by the free enthalpy change of a given reaction, and the kinetic stabilization related to the activation energy of a chosen chemical process
BDE(R-R) = E ( R -R ) -2SE(R') + S E ( R -R ) .
Eu(r) = a[ZSE(R') -SE(R-R)] + bThis analysis allowed us to give a new interpretation of the adjectives transient, persistent, and stable introduced by Griller and lngold and to show that the persistence of a radical may be due to other factors than steric ones. In conclusion, the concept of stabilization energy appears to be a good tool for rationalizing the static and dynamic properties of chemical species.
