This principle applies to reactions in which there is a lack of synchronization between
bond formation or bond rupture and other
primitive changes that affect the stability of products and reactants, such as
resonance,
solvation, electrostatic,
hydrogen bonding and
polarizability effects. The principle states that a product-stabilizing factor whose development
lags behind bond changes at the
transition state, or a reactant-stabilizing factor whose loss is ahead of bond changes at the
transition state, increases the
intrinsic barrier and decreases
the '
intrinsic rate constant' of a reaction. For a product-stabilizing factor whose development is ahead of bond
changes, or reactant factors whose loss lags behind bond changes, the opposite relations
hold. The reverse effects are observable for factors that destabilize a reactant or
product.
Source:
PAC, 1994, 66, 1077
(Glossary of terms used in physical organic chemistry (IUPAC Recommendations 1994))
on page 1170