Taft equation

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 Constants used in the Taft
equation[
organic compounds. 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
t Substituent Es σ*
equation is written as:
–H 1.24 0.49
–CH3 0 0

–CH2CH3 –0.07 –0.1

where is the ratio of the rate of the substituted reaction compared to the reference –CH(CH3)2 –0.47 –0.19

–C(CH3)3 –1.54 –0.3

reaction, σ* is the polar substituent constant that describes the field and inductive effects of
the substituent, Es is the steric substituent constant, ρ* is the sensitivity factor for the reaction to –CH2Ph –0.38 0.22
polar effects, and δ is the sensitivity factor for the reaction to steric effects.
–Ph –2.55 0.6
Polar substituent constants, σ*
Polar substituent constants describe the way a substituent will influence a reaction through polar (inductive, field, and resonance) effects.
To determine σ* Taft studied the hydrolysis of methyl esters (RCOOMe). The use of ester hydrolysis rates to study polar effects was first
suggested by Ingold in 1930.[6] The hydrolysis of esters can occur through either acid and base catalyzed mechanisms, both of which
proceed through a tetrahedral intermediate. In the base catalyzed mechanism the reactant goes from a neutral species to negatively charged
intermediate in the rate determining (slow) step, while in the acid catalyzed mechanism a positively charged reactant goes to a positively
charged intermediate.

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 σ* as:

where log(ks/kCH3)B is the ratio of the rate of the base catalyzed reaction compared to the reference reaction, log(ks/kCH 3)A is ratio of a rate
of the acid catalyzed reaction compared to the reference reaction, and ρ* is a reaction constant that describes the sensitivity of the reaction
series. For the definition reaction series, ρ* was set to 1 and R = methyl was defined as the reference reaction (σ* = zero). The factor of
1/2.48 is included to make σ* similar in magnitude to the Hammett σ values.

Steric substituent constants, Es

Although the acid catalyzed and base catalyzed hydrolysis of esters gives transition states for the rate determining steps that have differing
charge densities, their structures differ only by two hydrogen atoms. Taft thus assumed that steric effects would influence both reaction
mechanisms equally. Due to this, the steric substituent constant Es was determined from solely the acid catalyzed reaction, as this would not
include polar effects. Es was defined as:
 where ks is the rate of the studied reaction and is the rate of the reference reaction (R = methyl). δ is a reaction constant that describes
the susceptibility of a reaction series to steric effects. For the definition reaction series δ was set to 1 and Es for the reference reaction was set
to zero. This equation is combined with the equation for σ* 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]

Other steric parameters for LFERs

In addition to Taft’s steric parameter Es, other steric parameters that are independent of kinetic data have been defined. Charton has
defined values v that are derived from van der Waals radii.[9] Using molecular mechanics, Meyers has defined Va values that are derived
from the volume of the portion of the substituent that is within 0.3 nm of the reaction center.[10]

Sensitivity factors
Polar sensitivity factor, ρ*
Similar to ρ values for Hammett plots, the polar sensitivity factor ρ* for Taft plots will describe the susceptibility of a reaction series to polar
effects. When the steric effects of substituents do not significantly influence the reaction rate the Taft equation simplifies to a form of the
Hammett equation:

The polar sensitivity factor ρ* can be obtained by plotting the ratio of the measured reaction rates (ks) compared to the reference reaction (
) versus the σ* values for the substituents. This plot will give a straight line with a slope equal to ρ*. Similar to the Hammett ρ value:

If ρ* > 1, the reaction accumulates negative charge in the transition state and is accelerated by electron withdrawing groups.
If 1 > ρ* > 0, negative charge is built up and the reaction is mildly sensitive to polar effects.
If ρ* = 0, the reaction is not influenced by polar effects.
If 0 > ρ* > −1, positive charge is built up and the reaction is mildly sensitive to polar effects.
If −1 > ρ*, the reaction accumulates positive charge and is accelerated by electron donating groups.

Steric sensitivity factor, δ

Similar to the polar sensitivity factor, the steric sensitivity factor δ for a new reaction series will describe to what magnitude the reaction rate
is influenced by steric effects. When a reaction series is not significantly influenced by polar effects, the Taft equation reduces to:

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 δ. Similarly to the Hammett
ρ value, the magnitude of δ 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.
Since Es values are large and negative for bulkier substituents, it follows that:

If δ is positive, increasing steric bulk decreases the reaction rate and steric effects are greater in the transition state.
If δ is negative, increasing steric bulk increases the reaction rate and steric effects are lessened in the transition state.