The search for stable gas phase b(1) ions derived from aliphatic amino acids: a combined experimental and ab initio study

Abstract

Several previous studies have shown that b(1) ions (formally acylium ions, H(2)NCHRCO(+)) derived from protonated aliphatic amino acids are unstable in the gas phase, fragmenting via decarbonylation to form a(1) ions (iminium ions, H(2)N = CHR(+)). Herein we examine the fragmentation reactions of ten potential b(1) ion precursors to determine whether stable aliphatic b(1) ions can be formed in the gas phase. Of all the systems studied, only the aziridine b(1) ion and the dehydroalanine b(1) ion were found to be stable. These experimental results are entirely consistent with ab initio calculations (at the MP2(full)/6-311G** level) which indicate that while the loss of CO from the b(1) ion of glycine is barrierless and exoethermic, the related losses from the b(1) ions of aziridine and dehydroalanine have significant barriers (29.5 and 16.2 kcal mol(-1), respectively) and are endothermic overall.