Selected Es and * values[1] The Taft equation is a linear free energy relationship (LFER) used in physical organic chemistry in the study of reaction mechanisms and in the development of quantitative structure activity relationships for organic compounds. It was developed by Robert W. Taft in 1952[2][3][4] as a modification to the Hammett equation.[5] While the Hammett equation accounts for how field, inductive, and resonance effects influence reaction rates, the Taft equation also describes the steric effects of a substituent. The Taft equation is written as:
where log(ks/kCH3) is the ratio of the rate of the substituted reaction compared to the reference reaction, * is the polar substituent constant that describes the field and inductive effects of the substituent, Es is the steric substituent constant, * is the sensitivity factor for the reaction to polar effects, and is the sensitivity factor for the reaction to steric effects.
Contents
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1 Polar Substituent Constants, * 2 Steric Substituent Constants, Es o 2.1 Other Steric Parameters for LFERs 3 Sensitivity Factors o 3.1 Polar Sensitivity Factor, * o 3.2 Steric Sensitivity Factor, o 3.3 Reactions Influenced by Polar and Steric Effects 4 Taft Plots in QSAR
5 References
Due to the similar tetrahedral intermediates, Taft proposed that under identical conditions any steric factors should be nearly the same for the two mechanisms and therefore would not influence the ratio of the rates. However, because of the difference in charge buildup in the rate determining steps it was proposed that polar effects would only influence the reaction rate of the base catalyzed reaction since a new charge was formed. He defined the polar substituent constant * as:
where log(ks/kCH3)B is the ratio of the rate of the base catalyzed reaction compared to the reference reaction, log(ks/kCH3)A is ratio of a rate of the acid catalyzed reaction compared to the reference reaction, and * is a reaction constant that describes the sensitivity of the reaction series. For the definition reaction series, * was set to 1 and R = methyl was defined as the reference reaction (* = zero). The factor of 1/2.48 is included to make * similar in magnitude to the Hammett values.
where ks is the rate of the studied reaction and kCH3 is the rate of the reference reaction (R = methyl). is a reaction constant that describes the susceptibility of a reaction series to steric effects. For the definition reaction series was set to 1 and Es for the reference reaction was set to zero. This equation is combined with the equation for * to give the full Taft equation. From comparing the Es values for methyl, ethyl, isopropyl, and tert-butyl, it is seen that the value increases with increasing steric bulk. However, because context will have an effect on steric interactions[7] some Es values can be larger or smaller than expected. For example, the value for phenyl is much larger than that for tert-butyl. When comparing these groups using another measure of steric bulk, axial strain values, the tert-butyl group is larger.[8]
The polar sensitivity factor * can be obtained by plotting the ratio of the measured reaction rates (ks) compared to the reference reaction (kCH3) versus the * values for the substituents. This plot will give a straight line with a slope equal to *. Similar to the Hammett value:
If * > 1, the reaction accumulates negative charge in the transition state and is accelerated by electron withdrawing groups. If 1 > * > 0, negative charge is built up and the reaction is mildly sensitive to polar effects. If * = 0, the reaction is not influenced by polar effects. If 0 > * > -1, positive charge is built up and the reaction is mildly sensitive to polar effects. If -1 > *, the reaction accumulates positive charge and is accelerated by electron donating groups.
A plot of the ratio of the rates versus the Es value for the substituent will give a straight line with a slope equal to . Similarly to the Hammett value, the magnitude of will reflect to what extent a reaction is influenced by steric effects:
A very steep slope will correspond to high steric sensitivity, while a shallow slope will correspond to little to no sensitivity. If is negative, increasing steric bulk decreases the reaction rate and steric effects are greater in the transition state. If is positive, increasing steric bulk increases the reaction rate and sterics effects are lessened in the transition state.