Abstract: | Rate constants (k's) of the thermal cyclodimerization of ten meta-substituted trifluorostyrenes (m-Y-TFS's) have been measured in the temperature range 110–160°C. On the basis of these k's and the σmb values derived from 19F NMR data the spin-delocalization substituent constant σ˙m values of these ten meta-substituents have been calculated. The averaged σ˙m values are: m-Et, 0.09; m-t-Bu, 0.11; m-F, 0.03; m-Cl,?0.05; m-Br, 0.12: m-CF3, ?0.07; m-OMe, 0.10; m-NO2, ?0.002; m-CN, 0.11 and m-CO2Me, 0.08. Both the smallness of these values and the nonexistence of correlation between Hammett-Type polar σX and these σ˙m values support our belief that the σj?J approach is reliable and trustworthy. |