Kinetics and rate constants for reactions associated with organoborane autoxidations

Abstract

The thermal decomposition of the peroxides BuⁿOOBBuⁿ₂, (BuⁿOO)₂BBuⁿ, and (Bu^sOO)₂BBu^s occurs predominantly by a non-radical process with a low enthalpy and large negative entropy of activation. A minor homolytic decomposition was detected in vinyl acetate. The primary initiation, R₃B + O₂ [graphic omitted] radicals, was also investigated and k_i was found to be 1.7 ± 0.2 × 10^–5 for tri-s-butylborane; 0.9 ± 0.1 × 10^–5 for tri-isobutylborane, and ca. 6.8 × 10^–5 s^–1 for tricyclohexylborane.