Captodative effect free radicals

It has been postulated that the stability of free radicals is enhanced by the presence at the radical center of both an electron-donating and an electron-with-drawing group.This is called the push-pull or captodative effect (see also pp. 159). The effect arises from increased resonance, for example ... 

The concept of captodative substitution implies the simultaneous action of a captor (acceptor) and a donor substituent on a molecule. Furthermore, in the definition of Viehe et al. (1979), which was given for free radicals, both substituents are bonded to the same or to two vinylogous carbon atoms, i.e. 1,1- and 1,3-substitution, and so forth is considered. One might, however, also include 1,2-, 1,4-,. .. disubstitution, a situation which is more often referred to as push-pull substitution. Before discussing captodative substituent effects it might be helpful to analyse the terms capto and dative in more detail. 

Mutual conjugation of, as we describe it nowadays, + M and — M substituents is equivalent to an extra stabilization of the system. Thus, we can interpret this statement as the first formulation of the captodative effect even though the term was coined much later. The difficulty of organic chemists to comprehend the rather mathematically formulated theorem must have hindered its wider recognition and seems to be the reason that the phenomenon of interaction of -l-M and — M substituents has been reinvented several times since then. It is remarkable that these rediscoveries were always initiated by experimental studies in free radical chemistry. 

The familiarity with qualitative valence bond descriptions of substituent effects in combination with the known substituent effects in carbocations and carbanions led Viehe and his group to the postulate of a captodative effect for free radicals (Stella et ai, 1978 Viehe et al., 1979). They did not seem to be aware of the earlier work which was of a more physical organic character. The fact that carbocations [8] are stabilized by + M substituents, and carbanions [9] by - M substituents, raised the idea that free radicals, as... 

The first indication of the existence of a captodative substituent effect by Dewar (1952) was based on 7t-molecular orbital theory. The combined action of the n-electrons of a donor and a captor substituent on the total Jt-electron energy of a free radical was derived by perturbation theory. Besides the formulation of this special stabilizing situation and the quotation of a literature example [5] (Goldschmidt, 1920, 1929) as experimental evidence, the elaboration of the phenomenon was not pursued further, neither theoretically nor experimentally. 

If the reduction of C—C BDEs by captodative substitution is interpreted with the appropriate caution, it can be stated that a conclusive answer as to the existence of a captodative effect in free radicals cannot be derived from these studies, If, furthermore, a consequent error-propagation analysis had been carried out, the outcome might have been that the error limits do not allow a definitive conclusion. However, the results convey a feeling that— regardless of the pros and cons for the different determination procedures— a possible captodative effect will not be great. 

Several attempts have been made to analyse the captodative effect through rotational barriers in free radicals. This approach seems to be well suited as it is concerned directly with the radical, i.e. peculiarities associated with bond-breaking processes do not apply. However, in these cases also one has to be aware that any influence of a substituent on the barrier height for rotation is the result of its action in the ground state of the molecule and in the transition structure for rotation. Stabilization as well as destabilization of the two states could be involved. Each case has to be looked at individually and it is clear that this will provide a trend analysis rather than an absolute determination of the magnitude of substituent effects. In this respect the analysis of rotational barriers bears similar drawbacks to all of the other methods. 

The study of substituted allyl radicals (Sustmann and Brandes, 1976 Sustmann and Trill, 1974 Sustmann et al., 1972, 1977), where pronounced substituent effects were found as compared to the barrier in the parent system (Korth et al., 1981), initiated a study of the rotational barrier in a captodative-substituted allyl radical [32]/[33] (Korth et al., 1984). The concept behind these studies is derived from the stabilization of free radicals by delocalization of the unpaired spin (see, for instance, Walton, 1984). The... 

Have the numerous theoretical or experimental investigations shown evidence for the existence of a captodative effect in free radical chemistry If yes, what then is its magnitude ... 

The merits of the formulation of the captodative effect by Viehe lies in the fact that the numerous attempts to prove or disprove its existence have led to a better general understanding of substituent effects in free radical chemistry during the past decade. 

SUBSTITUENT EFFECTS ON FREE RADICALS. CAPTODATIVE EFFECTS... 

Discuss stabilization of free radicals by the captodative effect. [See, e.g., (a) Kosower,... 

Substituent effects on free radicals. Captodative effects 24... 

---