Subject: reference on structure-kinetics relationship

From: YONG HUANG <[email-masked]>
Date: Thu, 7 Mar 1996 21:48:20 -0600 (CST)

Can anybody recommend some literature (books, papers) on the relationship
between kinetics and molecular structure? The reason is as follows.

It seems easier to make a guess of stability, acidity or basicity etc. by
looking at the structure of a molecule than make a guess of how fast it would
react with other molecules. In other words, the relationship between
thermodynamics and structure is more straightforward than that between kinetics
and structure. However, the Hammett equation, as well as other physico-organic
equations, shows correlation between sigma (substituent parameter, a structural
parameter) and K, where this K can be either equilibrium constant or rate
constant. This implies thermodynamics goes the same way as kinetics in those
series of compounds. In my mass spectrometry experiment, it seems compounds of
even similar structure show different thermodynamic trend (acidity in my case)
than kinetic trend.* I think the bridge between thermodynamics and kinetics is 
the stability of reaction intermediate or activated complex. But I'm not
successful in making use of this knowledge to explain my experiments. Any 
help will be appreciated.

Yong
________________________
*E.g., in the chart of degree of proton transfer vs. acidity, sinapic acid and 
caffeic acid lie on the same line while 4-OH-cinnamic acid and ferulic acid on
the other line. The 2 lines may suggest 2 activation energies.