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.