Solutions of Li+ salts of highly alkylated derivatives of the monocarbadodecaborate anion in 1,2-dichloroethane catalyze the radical polymerization of simple terminal alkenes, dienes, and alkynes under ambient conditions, initiated by azoisobutyronitrile, di-tert-butyl peroxide, or atmospheric air.

Density functional theory was employed to calculate the acidities and hydride abstraction enthalpies of propene (3) and propane (4), along with their vinylogues (5 and 6, respectively). The same reaction enthalpies were calculated for the propene vinylogues in which the terminal vinyl group was rotated perpendicular to the rest of the conjugated system (7). The contribution by resonance and inductive effects toward the acidity and hydride abstraction enthalpy of each vinylogue of 5 (n = 1-3) was computed and extrapolated to n = 0 (the parent propene system). The resonance energies of the allyl cation and anion were determined to be about 20-22 and 17-18 kcal/mol, respectively. Comparisons are made to resonance energies calculated using other methodologies.

Relative gas‐phase acidities of para‐substituted phenols (1, Sub—C6H4—OH) and their ω‐substituted para‐alkylphenol analogs [2, Sub—(CH2)n—C6H4—OH] were calculated at the B3LYP/6–31+G* and AM1 levels of theory. The acidity of a substituted molecule of 2 is compared with that of the unsubstituted molecule of 2 to determine the field/inductive effect of the substituent on the acidity of 2. This field/inductive effect was extrapolated to n = 0, yielding the field/inductive effect of the substituent on the acidity of 1. The derived field/inductive effect in 1 was subtracted from the difference in acidity between 1 and phenol in order to determine the resonance effect of the substituent on the acidity of 1. Our results are compared with the field/inductive and resonance substituent parameters empirically derived from previous experimental solution studies. Copyright © 2004 John Wiley & Sons, Ltd.

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