ISSN:
0894-3230
Keywords:
Organic Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
,
Physics
Notes:
The effect of substituents on the rate of a reaction and the effect of the same substituents on the equilibrium can often be related by a linear free energy relation (LFER): log k- = α log K= + constant, where k+ and K= are the rate constant and the equilibrium constant, respectively. This review, concentrating on group transfers, adds to many studies describing the use of α to describe the transition state. Although the use of α to describe transition states is general, group transfers constitute a simple class allowing a fairly complete description yet illustrating two often neglected contributions. Group transfers can be described by the Marcus equation relating rate to an average identity rate and the equilibrium constant; a major contributor to the slope, α, of the rate-equilibrium LFER is the variation of identity rates with substituent, rather than reflecting product-like character. Substituent effect LFERs are predominantly attributable to interaction of charges with the substituent. However, α is not an exact measure of the charge on the substituent-containing group, because in a transition state, but often not in a reaction product, there are more remote centers of charge which exert a smaller attenuated effect. A simple treatment of this attenuation for group transfers is proposed. The possibility of application of these ideas to proton transfer reactions and the interpretation of the Brønsted α (or β) is proposed.
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/poc.610030102
