Isomeric [C,H3,N,O]+˙ ions and their neutral counterparts

✍ Scribed by Cornelis E. C. A. Hop; Hongwen Chen; P. J. A. Ruttink; John L. Holmes

• Publisher: John Wiley and Sons
• Year: 1991
• Tongue: English
• Weight: 827 KB
• Volume: 26
• Category: Article
• ISSN: 1076-5174
• DOI: 10.1002/oms.1210260803

✦ Synopsis

Abstract

The isomeric ions [H~2~NC(H)O]^+^˙, [H~2~NCOH]^+^˙, [H~3~CNO]^+^˙ and [H~2~CNOH]^+^˙ were examined in the gas phase by mass spectrometry. Ab initio molecular orbital theory was used to calculate the relative stabilities of [H~2~NC(H)O]^+^˙, [H~2~NCOH]^+^˙, [H~3~NCO]^+^˙ and their neutral counterparts. Theory predicted [H~2~NC(H)O]^+^˙ to be the most stable ion. [H~2~NCOH]^+^˙ ions were generated via a 1,4‐hydrogen transfer in [H~2~NC(O)OCH~3~]^+^˙, [H~2~NC(O)C(O)OH]^+^˙ and [H~2~NC(O)CH~2~CH~3~]^+^˙. Its metastable dissociation takes place via [H~3~NCO]^+^˙ with the isomerization as the rate‐determining step. [H~2~CNOH]^+^˙ undergoes a rate‐determining isomerization into [H~3~CNO]^+^˙ prior to metastable fragmentation. Neutralization‐reionization mass spectrometry was used to identify the neutral counterparts of these [H~3~,C,N,O]^+^˙ ions as stable species in the gas phase. The ion [H~3~NCO]^+^˙ was not independently generated in these experiments; its neutral counterpart was predicted by theory to be only weakly bound.