Substituents effect on stability

Table 12.5. Substituent Effects on Stability of AilyUc and Benzyiic Radicals from Theoretical Calculations of Radical Stabilization Energies...

Sung, K. Substituent effects on stability of oxiranes, oxirenes, and dioxiranes. Can. J. Chem. 2000, 78, 562. 

Substituent effects on stability of a carbocation can be estimated from the following isodesmic reactions (Figure 6.43, performed at HF/6-31G level). Again, stabilization energies have a clearly manifested stereoelectronic component as illustrated by differences in stabilization energies imposed by substituents in the eclipsed and perpendicular conformations. 

Carbanions are quite useful in synthesis, since formation of new carbon-carbon bonds often requires a nucleophilic carbon species. There has therefore been a good deal of study on methods of generating carbanionic species and on understanding substituent effects on stability and reactivity. 

Because carbocations are key intermediates in many nucleophilic substitution reactions, it is important to develop a grasp of their structural properties and the effect substituents have on stability. The critical step in the ionization mechanism of nucleophilic substitution is the generation of the tricoordinate carbocation intermediate. For this mechanism to operate, it is essential that this species not be prohibitively high in energy. Carbocations are inherently high-energy species. The ionization of r-butyl chloride is endothermic by 153kcal/mol in the gas phase. ... 

Table 8.5. Substituent Effects on Carbonyl Group Stabilization...

Similarly, carboxylic acid and ester groups tend to direct chlorination to the / and v positions, because attack at the a position is electronically disfavored. The polar effect is attributed to the fact that the chlorine atom is an electrophilic species, and the relatively electron-poor carbon atom adjacent to an electron-withdrawing group is avoided. The effect of an electron-withdrawing substituent is to decrease the electron density at the potential radical site. Because the chlorine atom is highly reactive, the reaction would be expected to have a very early transition state, and this electrostatic effect predominates over the stabilizing substituent effect on the intermediate. The substituent effect dominates the kinetic selectivity of the reaction, and the relative stability of the radical intermediate has relatively little influence. 

Substituent effects on spin preference and kinetic stabilities... 

An EPR study of the monomeric 02 adducts of the Schiff base complexes of Co(bzacen)(py) (71a) and the thiobenzoyl analog Co(Sbzacen)(py) (71b) characterized the five-coordinate mono (pyridine) precursors and the six-coordinate 02 adducts.327 Increased covalency in the Co—S bonds was seen in the EPR parameters, indicative of 7r-backbonding. Substituent effects on the aromatic rings had no effect on the EPR spectra, but these were reflected in the observed redox potentials. Furthermore, the S-donors stabilize the Co ion in lower oxidation states, which was consistent with destabilization of the 02 adducts. 

Although an explanation for the substituent effects on the thermal stability of the thiepin ring awaits further systematic studies, an attractive way of explaining these effects would be a concept of "effective descontinuity of cyclic conjugation proposed recently by Inagaki ... 

In this article, a description has been given of recent investigations in the field of thiepin chemistry which are important for the major seven-membered unsaturated heterocyclic compounds. While the properties of these sulfur heterocycles have been determined quite well, some important questions still remain unexplored. Our current research efforts involve attempts to understand more generally the substituent effects on the thermal stability of the thiepin. 

Substituent effect on the stability of the transition state for solvent addition (C, Figure 6). The difference in the values of ks = 1.4 x 107s 1 for the addition of a solvent of 50/50 (v/v) trifluoroethanol/water to Me-[10+] and ks = 1.0 x 109 s-1 for addition of the same solvent to Me-[8+] (Table 1) reflects the balance between (1) the destabilization of X-[10+] resulting from rotation about the —Ca bond, which results in a less stable carbocation and hence an... 

Substituent effect on the stability of the transition state for deprotonation (D, Figure 6). The addition of two ortho-methyl groups to Me-[8+] to give Me-[10+] results in an increase in kp for proton transfer to solvent from 1.4 x 106 s 1 to 8.3 x 107 s 1 (Table 1). There should be relatively little steric hindrance to the reaction of solvent with the /1-hydrogens of Me-[10+] because these are relatively distant from the ortho-methyl groups. However, the twisting about the CAr-Ca bond that minimizes steric interactions between the methyl... 

It is of interest to consider the form of the Bronsted plot or Eigen plot to be expected for reaction of a series of related intramolecularly hydrogen-bonded acids with hydroxide ion by the mechanisms in Schemes 5 and 6. The effect of a substituent on the value of the dissociation constant of an intramolecularly hydrogen-bonded acid (8 log K) will be two-fold. The stability of the undissociated acid will be modified because of a substituent effect on the... 

We have reported the synthesis of a series of azulene-substituted methyl cations, i.e., tri(l-azulenyl)methyl, di(l-azulenyl)phenylmethyl, and (1-azul-enyl)diphenylmethyl cations (2a+, 3a+, and 4a+) (Figure 6) (6). In order to examine substituent effects on the azulene rings and to enhance their stabilities, a series of the cations (2b-d+, 3b-d, and 4b-d+) bearing tert-buty groups on each azulene ring were also synthesized (7). 

Model computational studies aimed at understanding structure-reactivity relationships and substituent effects on carbocation stability for aza-PAHs derivatives were performed by density functional theory (DFT). Comparisons were made with the biological activity data when available. Protonation of the epoxides and diol epoxides, and subsequent epoxide ring opening reactions were analyzed for several families of compounds. Bay-region carbocations were formed via the O-protonated epoxides in barrierless processes. Relative carbocation stabilities were determined in the gas phase and in water as solvent (by the PCM method). 

One point of debate in defining the magnitude of the captodative effect has been the separation of substituent effects on the radical itself as compared to that on the closed shell reference system. This is, as stated before, a general problem for all definitions of radical stability based on isodesmic reactions such as Eq. 1 [7,74,76], but becomes particularly important in multiply substituted cases. This problem can be approached either through estimating the substituent effects for the closed shell parents separately [77,78], or through the use of isodesmic reactions such as Eq. 5, in which only open shell species are present ... 

Substituent effect on the kinetic stability (4(7 in kcal mol-1 at Tc) of RNH3C104 complexes of crown ethers [257] in CD2C12 ... 

F. G. Bordwell, J.-P. Cheng. Substituent Effects on the Stabilities of Phenoxyl Radicals and the Acidities of Phenoxyl Radical Cations. J. Am. Chem. Soc. 1991, 113, 1736-1746. 

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