Electronic effects separated from steric

Why is the exchange phenomenon limited to primary alcohols and is there an electronic effect separate from the steric effect ... 

It has to date been recognized that the breaking and forming of bonds in solution are in principle influenced by three major factors electronic, steric and solvent effects. Thus, in a quantitative examination to differentiate covalent and ionic bond formation, it is necessary first to investigate the electronic effect alone, separate from steric and solvent effects. 

Two separate computational investigations of the Rh/dppms catalyst and related systems have appeared in the literature. One study [40] concluded that steric effects were important in promoting migratory CO insertion in [Rh(CO)(dppms)l2Me], while the other [41] proposed that an electronic effect, arising from the sulfur donor atom of dppms, was responsible. It is likely that a combination of steric and electronic effects result in the observed reactivity. 

The estimate of relative stabilities via the comparison of total strain energies is in general limited to a series of conformers and isomers (see for instance Chapter 7 and the relevant chapters in Parts I and III). The determination by molecular mechanics calculations of relative stabilities of a series of complexes with metal ions having differing geometric preferences (electronic effects) and preferences in terms of donor atoms is therefore a questionable approach. A comparative study is only useful if the structural preferences of the different metal ions are similar and/or if the electronic effects may be separated from steric effects. 

Taft began the LFER attack on steric effects as part of his separation of electronic and steric effects in aliphatic compounds, which is discussed in Section 7.3. For our present purposes we abstract from that treatment the portion relevant to aromatic substrates. Hammett p values for alkaline ester hydrolysis are in the range +2.2 to +2.8, whereas for acid ester hydrolysis p is close to zero (see Table 7-2). Taft, therefore, concluded that electronic effects of substituents are much greater in the alkaline than in the acid series and. in fact, that they are negligible in the acid series. This left the steric effect alone controlling relative reactivity in the acid series. A steric substituent constant was defined [by analogy with the definition of cr in Eq. (7-22)] by Eq. (7-43), where k is the rate constant for acid-catalyzed hydrolysis of an orr/to-substituted benzoate ester and k is the corresponding rate constant for the on/to-methyl ester note that CH3, not H, is the reference substituent. ... 

The ortho effect may consist of several components. The normal electronic effect may receive contributions from inductive and resonance factors, just as with tneta and para substituents. There may also be a proximity or field electronic effect that operates directly between the substituent and the reaction site. In addition there may exist a true steric effect, as a result of the space-filling nature of the substituent (itself ultimately an electronic effect). Finally it is possible that non-covalent interactions, such as hydrogen bonding or charge transfer, may take place. The role of the solvent in both the initial state and the transition state may be different in the presence of ortho substitution. Many attempts have been made to separate these several effects. For example. Farthing and Nam defined an ortho substituent constant in the usual way by = log (K/K ) for the ionization of benzoic acids, postulating that includes both electronic and steric components. They assumed that the electronic portion of the ortho effect is identical to the para effect, writing CTe = o-p, and that the steric component is equal to the difference between the total effect and the electronic effect, or cts = cr — cte- They then used a multiple LFER to correlate data for orrAo-substituted reactants. 

Structure analysis has shifted completely from intramolecular to intermolecular structure. Distributions of intermolecular distances can be statistically analyzed over hundreds of thousands of reliable data these distributions should be properly normalized to be statistically significant. The chemical interpretation must, however, take into account the unavoidable fact that intermolecular separations are a combination of steric and electronic effects, and that near to does not always mean bound to . 

Evaluation of steric effects can also be made by separating electronic from steric effects with the help of linear free energy relationship and appropriate parameters. Applications of the Hammett equation to heterocycles have been reviewed (64AHC(3)209 76AHC(20)1) and the influence of substituent effects on the basicity and N-alkylation of pyridines, which have been by far the most widely studied, shows the difficulties in this approach. Jaffe and Jones (64AHC(3)209) reported a good correlation between pKA of 3- and 4-substituted pyridines and Hammett a parameters ([Pg.179]

The conformational behavior of these compounds involves several steric and 7r-barriers separating twisted or folded intermediates. The similarity in steric and Tt-barriers makes it difficult to separate steric from electron effects. 

Electronic effects on alkene regioselectivity in the Pauson-Khand reaction have also been observed. The regioselectivity observed in cycloadditions of norbomen-2-ones has been interpreted as arising from an electronic preference for attachment of the 5 C-S of the alkene to an alkyne carbon rather than cobalt in the bond-forming insertion step (equation 13). In these systems electronic and steric effects have been separated by carrying out identical reactions with the corresponding norbomen-2-ols, in which the... 

In principle, extrathermodynamic relationships that deviate from the simple Hammett equation (equation 8) can be treated by equation 14. The major problem is the determination of the different sets of o s, (e.g., set and 0 set) in a way that will indeed reflect their relation to independent properties. An example of such a procedure is the separation of polar and steric effects (10). The need for such a separation arose when a nearly complete lack of correlation was observed between substituent effects represented by the Hammet a constants and the rates for alkaline hydrolysis of aliphatic systems (12). Inspection of the structures indicated that the proximity of the substituents to the reaction site was a common feature. The steric interaction between R and X had to be considered separately from the electronic effects. Polar substituent constants were thus defined as the difference between the rate constants of base and acid catalyzed hydrolysis of esters. From the structural similarity of the transition states for these reactions (equation 15) it was assumed that the difference in their charge reflects only the polar effect of the substituent... 

Clearly the first approximation does not generate a universal ir scale for substituents that is independent of the system from which they have been derived. Just as multiple o scales have been derived to represent different electronic effects in different molecular systems (section A.1 above), so several tt scales are needed to represent different solvations in different molecular systems. Alternatively, a separation of the effects (electronic and steric) that could contribute to the observed tt values can be attempted, assuming that they are independent and additive. 

In the early 1950s Taft (10) outlined a sound quantitative basis for the estimation of steric effects and for separating them from polar and resonance effects. This derivation follows the standard extrathermodynamic approach and is therefore empirical. The definition of steric substituent constants is closely related to polar substituent constants, for they are obtained from the same reference system (10). The polar substituent constants, however, have been shown to arise from electronic effects, and they strongly correlate with the inductive substituent constants (10, 43, 61). 

The negative sigma coefficient in eq 26 indicates that electron withdrawing groups are unfavorable. But it isn t clear from this equation that this is due to an unfavorable effect on distribution and that the a component relating to mechanism is positive (i.e. a +a corresponds to a -pKg term in eq 25). ortho-Derivatives required an E term. Since ortho substitution also reduces acidity, the true influence of steric factors on uncoupling, separated from influences on acidity-distribution, can only be determined by using E with log D. 

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