Hydrogen and carbon scrambling in C4H9 + cations reacting by methane loss in the gas phase: equilibration of n-, iso-, s-, and t-butyl cations undergoing metastable transitions

Abstract

The C₄H₉ ⁺ cations generated from CH₃·CH₂·CH₂·CH₂X systems have been shown to undergo complete scrambling of both the carbon and hydrogen atoms before methane loss with a rate constant in the region 10⁵–10⁶ sec.^–1. The C₄H₈˙⁺ radical-cations, generated from the same types of system, have been shown to undergo complete or almost complete hydrogen scrambling before methyl radical loss with a rate constant in the region 10⁵–10⁶ sec.^–1. The C₄H₉ ⁺ cations generated from n-, iso-, s-, and t-butyl structures have isomerized completely, or almost completely, to the same structure, or mixture of structures, before loss of ethylene or methane with the rate constants given above.