Unimolecular Rearrangements of Transient Carboxy Radicals and Cations

Abstract

Charge reversal (CR) and neutralization–reionization (NR) mass spectra of aliphatic carboxylate ions RCOO– provide insight into the behaviour of the transient neutral carboxy radicals RCOO• as well as the short-lived RCOO+ cations. For the neutral radicals, a novel hydrogen rearrangement is proposed, which might explain the sometimes only modest yields in the Hunsdiecker reaction of carboxylic acids in the condensed phase.