Abstract
The nucleophile-initiated polymerization of α, α-disubstituted β-lactones (R, R'-BPL) was studied with the extended Hückel molecular orbital theory.
First, the results of the calculations well explained the experimental findings concerning the reaction course between acid or base catalyst and R, R'-BPL. Secondly, relatively small overlap population of the β-C-O bond in the lactone ring, 0.43∼0.47, suggests weakness of this bond. There exists a parallelism between the overlap population of the above bond in R, R'- BPL and the initial rate constant (k1) of the reaction of R, R'-BPL initiated by quaternary ammonium carboxylates. Finally, we discussed the reactivity of R, R'-BPL toward strong base catalysts.
