jo702492r_si_001.pdf (212.69 kB)
Rapid Formation and Slow Collapse of a Carbocation−Anion Pair to a Neutral Molecule
journal contribution
posted on 2008-01-04, 00:00 authored by Weifang Hao, Vernon D. ParkerThe 4,4‘,4‘ ‘-trimethoxytrityl cation (TMT+) was observed to react with acetate ion in acetic acid reversibly
to give the corresponding ester (TMT-OAc). The rate of the reaction was found to be independent of
[NaOAc] over a 25000-fold range. Similar results were observed in the presence of Bu4N+ in acetic acid
as well as in HOAc/AN (1/1). It was concluded that {TMT+ (HOAc/AcO-)} is an ion pair that forms
essentially completely from free TMT+ and HOAc/AcO- during the time of mixing under stopped-flow
conditions. The process which was studied kinetically is the intramolecular collapse of the ion pair to
TMT-OAc which takes place in two steps involving a kinetically significant intermediate. The remarkably
close resemblance of this reaction to the Winstein scheme for solvolysis reactions is noted. In analogy
to the Winstein scheme, it was proposed that the intermediate could be an intimate ion pair formed upon
extrusion of solvent from the solvent separated ion pair. The product-forming step could then correspond
to the intimate ion pair reacting further to form a covalent bond between the two moieties within the
complex. The values of the thermodynamic and the activation parameters as well as the apparent rate
constants for the reaction in the presence of either sodium or tetrabutylammonium ions suggest that
these counterions play insignificant roles in the reactions. However, the equilibrium constant for the
intramolecular step (K4) was observed to be two times greater in the presence of Bu4N+ than in the
presence of Na+. The rate of the reaction in HOAc was observed to be about four times as great as that
in HOAc/AN (1/1).