Electrophilicities of symmetrically substituted 1,3-diarylallyl cations

Kinetics of the reactions of nine symmetrically substituted 1,3-diarylallyl cations with different nucleophiles were studied photometrically in dichloromethane, acetonitrile, and DMSO solutions. The second-order rate constants k(2) were found to follow the correlation log k(2) = s(N)(N + E). The electrophilicity parameters E of the title cations were derived, using the known values of s(N) and N of the nucleophilic reaction partners, and compared with the electrophilicities of analogously substituted benzhydrylium ions. Good linear correlations were found between the electrophilicities E and the quantum chemically calculated gas-phase methyl anion affinities of the allyl cations and the σ(+) constants of the substituents X.     

Addition reactions of carbocations with alkenes: Studies on the mechanism of carbocationic polymerization

In certain cases, Lewis acid catalyzed addition reactions of alkyl halides with alkenes terminate at the 1:1 product stage. This telomerization reaction has been employed to study the efficiency of initiating systems of carbocationic polymerization and the relative reactivities of alkenes towards carbenium ions. A direct determination of addition rate constants is possible in some cases.     

Reactivities of Carbocations and Carbanions

Initiation and propagation rate constants of carbocationic and carbanionic polymerizations can be predicted by the correlation equation log k_{20 °C} = s(N + E), where E characterizes the electrophilicity of carbocations and electron-deficient alkenes, and N characterizes the nucleophilicity of carbanions and electron-rich alkenes. Since the nucleophile-specific slope parameter s is generally close to 1, it can be neglected in a first approximation, and the two-dimensional representation in Figure 3 illustrates the gradual change from carbanionic to carbocationic polymerizations with Hall's “initiation by bond-formation” as the link connecting the two ranges. The value of model studies for understanding ionic polymerizations is illustrated.