Resonance energy allyl radical

Allyl and benzyl radical are substantially stabilized, as anticipated from the resonance structures (see Section 1.3.6). Comparing the BDEs of propene and toluene to an appropriate reference such as ethane suggests resonance stabilization energies of 12.4 and 14.1 kcal / mol, respectively. An alternative way to estimate allyl stabilization is to consider allyl rotation barriers (Eq. 2.12). Rotating a terminal CH2 90° out-of-plane completely destroys allyl resonance, and so the transition state for rotation is a good model for an allylic structure lacking resonance. For allyl radical the rotation barrier has been determined to be 15.7 kcal / mol, in acceptable agreement with the direct thermochemical number. 

Resonance theory can also account for the stability of the allyl radical. For example, to form an ethylene radical from ethylene requites a bond dissociation energy of 410 kj/mol (98 kcal/mol), whereas the bond dissociation energy to form an allyl radical from propylene requites 368 kj/mol (88 kcal/mol). This difference results entirely from resonance stabilization. The electron spin resonance spectmm of the allyl radical shows three, not four, types of hydrogen signals. The infrared spectmm shows one type, not two, of carbon—carbon bonds. These data imply the existence, at least on the time scale probed, of a symmetric molecule. The two equivalent resonance stmctures for the allyl radical are as follows ... 

The observation that in the case of PCSO there is no formation of propanol while allyl alcohol is formed from ACSO agrees with the resonance stabilization of the allyl radical and hence weaker bond for S-allyl than for S-propyl. The yield of allyl alcohol from irradiation of ACSO is considerably greater than that from S-allyl-L-cysteine, probably due to energy delocalization by the four p electrons of the S atom. 

When considering the stability of spin-delocalized radicals the use of isodesmic reaction Eq. 1 presents one further problem, which can be illustrated using the 1-methyl allyl radical 24. The description of this radical through resonance structures 24a and 24b indicates that 24 may formally be considered to either be a methyl-substituted allyl radical or a methylvinyl-substituted methyl radical. While this discussion is rather pointless for a delocalized, resonance-stabilized radical such as 24, there are indeed two options for the localized closed shell reference compound. When selecting 1-butene (25) as the closed shell parent, C - H abstraction at the C3 position leads to 24 with a radical stabilization energy of - 91.3 kj/mol, while C - H abstraction from the Cl position of trans-2-butene (26) generates the same radical with a RSE value of - 79.5 kj/mol (Scheme 6). The difference between these two values (12 kj/mol) reflects nothing else but the stability difference of the two parents 25 and 26. 

On the basis of this mechanism the difference in the energy of activation for the decomposition to isoprene and that for the decomposition of isopropylcyclobutane to 3-methylbutene-l should equal the allyl radical resonance energy. The value obtained in this fashion is 11-6 +1 kcal mole in close agreement with the values obtained by other methods. 

Previous discussions (20, 39) on the propagation rate, kp, point out the effect caused by the resonance energy of the radical formed. Our results support this view and enable us to complete the arrangement by families according to the groups adjacent to the attacked function—alkyl, benzyl, alkoxy, allyl, hydroxyl. The steric effect does not reveal itself in any important way—e.g., a-methylbenzylic ether has a kp which is close to that of benzylic ether, and the tertiary carbons in the former product are generally attacked at rates comparable with that of a less-encumbered carbon. 

About the same value, 25 kcal/mole, is found for the resonance energy of the allyl radical 6 the resonance energy stabilizing the product is that... 

We may perform the same analysis for the allyl radical and the allyl anion, respectively, by adding the energy of 4>2 to the cation with each successive addition of an electron, i.e., H (allyl radical) = 2(a + V2/3) + a and Hn allyl anion) = 2(a + s/2f) + 2a. In the hypothetical fully 7T-localized non-interacting system, each new electron would go into the non-interacting p orbital, also contributing each time a factor of a to the energy (by definition of o ). Thus, the Hiickel resonance energies of the allyl radical and the allyl anion are the same as for the allyl cation, namely, 0.83/1. 

Benzene and other aromatics alike are stable molecules, while cyclobutadiene and other antiaromatic molecules are unstable molecules.27-76 Similarly, allylic species are stable intermediates and possess significant rotational barriers. It may appear as a contradiction that, for example, the tr-component of benzene can be distortive but it still endows the molecule with special stability or that the distortive jr-component of allyl radical can lead to a rotational barrier. We would like to show in this section that these stability patterns derive from the vertical resonance energy which is expressed as a special stability because for most experimental probes (in eluding substitution reactions) the o-frame restricts the molecule to small distortion167 in which the vertical resonance energy is still appreciable, as shown schematically in Figure 5. 

Shaik and Bar102 demonstrated that allyl anion has a distortive jr-component but at the same time exhibits a rotational barrier. This analysis was reaffirmed later for allyl radical.5 Subsequently, Gobbi and Frenking93 pointed out that the total distortion energy of allylic species is very small because it reflects the balance of jr-distortivity opposed by the a-symmetrizing propensity. They further argued that along with this jr-distortivity, the allylic species enjoys resonance stabilization which is the source of the rotational barrier. A detailed VB analysis by Mo et al.149 established the same tendency. 

Figure 9. Hess cycle used to relate the rotational barrier of allyl radical to its resonance energy. All energies are given in kcal/mol (data for the cycle is taken from ref 93 B values from ref 111).

As mentioned with benzyl groups, an allylic center is also quite susceptible to autoxidation chemistry (Fig. 109). The allylic hydrogen has a weak C-H bond dissociation energy due to the resonance stabilization energy of the resulting allylic radical (157). 

In an ESR study of 1,1,3,3-difluoroallyl radicals, Krusic and coworkers were able to demonstrate that the barrier to rotation of such apparently planar radicals is substantially reduced [18]. Although allyl itself has a rotational barrier of 15 kcal/mol [19, 20], 1,1,3,3-tetrafluoroallyl, 1, had a barrier of but 7.2 kcal/mol. The observed 19F hfs constants (42.6 and 39.7 G) were consistent with 1 being a planar system. It is likely that the lowering of the rotational barrier of 1 derives from a destabilizing interaction between the fluorine lone pairs and the doubly-occupied allyl tt-MO which diminishes the net allylic resonance energy, as well as from stabilization of the transition state due to pyramidalization. 

A curious effect, prone to appear in near degeneracy situations, is the artifactual symmetry breaking of the electronic wave function [27]. This effect happens when the electronic wave function is unable to reflect the nuclear framework symmetry of the molecule. In principle, an approximate electronic wave function will break symmetry due to the lack of some kind of non-dynamical correlation. A typical example of this case is the allyl radical, which has C2v point group symmetry. If one removes the spatial and spin constraints of its ROHF wave function, a lower energy symmetry broken (Cs) solution is obtained. However, if one performs a simple CASSCF or a SCVB [28] calculation in the valence pi space, the symmetry breaking disappears. On the other hand, from the classical VB point of view, the bonding of the allyl radical is represented as a superposition of two resonant structures. 

The CH bond in propene is weaker than the CH bond of ethane because the allyl radical is stabilized by resonance. The ethyl radical has no such resonance stabilization. The difference between these bond dissociation energies provides an estimate of the resonance stabilization of the allyl radical 13 kcal/mol (54 kJ/mol). 

Although free-radical halogenation is a poor synthetic method in most cases, free-radical bromination of alkenes can be carried out in a highly selective manner. An allylic position is a carbon atom next to a carbon-carbon double bond. Allylic intermediates (cations, radicals, and anions) are stabilized by resonance with the double bond, allowing the charge or radical to be delocalized. The following bond dissociation enthalpies show that less energy is required to form a resonance-stabilized primary allylic radical than a typical secondary radical. 

In these two latter cases it appears with certainty from the heat of combustion and from spectra that there is nothing special about the bonds themselves. The low dissociation energy must, therefore, find its cause in the special stability of the products of dissociation, in these cases the allyl radical. The particular stability of this radical follows from the resonance which is possible here between two equivalent configurations. H2C=CH— GH2 H2C—GH=GH2... 

The resonance energy of the allylic radical is 48.8 kJ mol-1 [57, 58]. It is easily formed and its reactivity is low. It reacts reluctantly with monomers. This is why propene, 2-methylpropene, 1-butene (and higher members of the homologous series) do not polymerize by the radical mechanism... 

A further, most important outcome of the resonance theory is this as a resonance hybrid, the allyl radical is more stable (i.e., contains less energy) than either of the contributing structures. This additional stability possessed by the molecule is referred to as resonance energy. Since these particular contributing structures are exactly equivalent and hence of the same stability, we expect stabilization due to resonance to be large. 

Just how large is the resonance energy of the allyl radical To know the exact value, we would have to compare the actual, hybrid allyl radical with a non-existent radical of structure I or II—something we cannot do, experimentally. We can, however, estimate the resonance energy by comparing two reactions dissociation of propane to form a /i-propyl radical, and dissociation of propylene to form an allyl radical. 

Propane, the /j-propyl radical, and propylene are each fairly satisfactorily represented by a single structure the allyl radical, on the othei hand, is a resonance hybrid. We see that the energy difference between propylene and ific allyl radical is 10 k al/ niole less (98 - 88) than the energy difference between propane and the... 

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