PERICYCLIC REACTIONS IN THERMAL PYROLYSIS OF POLYCARBODIIMIDE

摘要

Experimental data from polycarbodiimide pyrolysis are interpreted as proceeding by pericyclic steps that generate the monomer. Electronic structure calculations at Hartree-Fock and semiempirical levels were used for predicting reaction thermochemistry and kinetics. Although bond dissociation energies were too strong to explain the pyrolysis kinetics, the activation energy for a six-electron pericyclic transition state was lower and consistent with the data.