Journal of Physical Chemistry B, Vol.107, No.1, 298-305, 2003
Kinetic studies on the reactivity of triphenylmethyl cations adsorbed on silica, alumina, and aluminosilicate
The apparent rate constants k' of different surface-mediated reactions of three nucleophiles 1,4-cyclohexadiene, triethylsilane, and isobutylvinyl ether with triphenylmethylium ions have been determined for three different solid acid catalysts and various triphenylmethylium precursors ((RRRC)-R-1-R-2-C-3-X, X = SCN, OH, Cl, or Br). Generation of triphenylmethylium ions [(RRRC+)-R-1-R-2-C-3] was used for kinetic measurements when (RRRC)-R-1-R-2-C-3-X derivates are chemisorbed to the solid acid catalysts. The catalysis of those surface-mediated reactions by a silica, an alumina, and an aluminosilicate has been studied in a slurry of dichloromethane at ambient temperature. The value of V increases in the order OH- < SCN- < Cl- < Br- and silica < alumina < aluminosilicate. The log k' can be correlated with the pK(s) of the corresponding HX from (RRRC)-R-1-R-2-C-3-X or the acidity of the solid acid (Adolph, S.; Spange, S.; Zimmermann, Y. J. Phys. Chem. B 2000, 104, 6429-6438) indicating the importance of the effective surface concentration of [(RRRC+)-R-1-R-2-C-3] on the apparent rate constant. It is also shown that the specific rate constant of the surface-mediated reaction can be interpreted in terms of Mayr's nucleophilicity parameters of the π-nucleophile (N) and the pK(R)+ values of the carbenium ion derived from polar reactions in homogeneous solution.