Abstract

European Journal of Mass Spectrometry
Volume 15 Issue 2, Pages 91–104 (2009)
doi: 10.1255/ejms.952

Anions [N(CH2)3]– and [ON(CH2)2]– are stable in the gas phase, but can they be charge stripped to form the radicals N(CH2)3 and ON(CH2)2? A joint experimental and theoretical study

Mark Fitzgerald, Suresh Dua, Daniel Bilusich, Peter C.H. Eichinger, Salvatore Peppe and John H. Bowie*
Department of Chemistry, The University of Adelaide, South Australia, 5005. E-mail: john.bowie@adelaide.edu.au

Collision-induced activation of deprotonated trimethylamine N-oxide yields the two anions [N(CH2)3]– and [ON(CH2)2]– following losses of H2O and CH4, respectively. These two anions decompose by minor losses of H• and H2 when collisionally activated: no other fragmentations are noted. Calculations at the CCSD(T)/aug-cc-pVDZ//B3LYP/6-31+G(d) level of theory indicate that these trigonal anions are stable, and should not rearrange following collisional activation. Collisional-induced charge stripping of the anions [N(CH2)3]– and [ON(CH2)2]–, respectively, form N(CH2)3 and ON(CH2)2. Some of these neutrals are energised and undergo rearrangement and dissociation. From a consideration of experiment and theory, it is proposed (i) that energised N(CH2)3 may cyclise to form the 1-aziridinylcarbinyl radical. This species may ring open to CH2=NCH2CH2 which then decomposes to CH2N and C2H4 and (ii) energised ON(CH2)2 may undergo OC cyclisation followed by ring opening to energised CH2=NCH2O which may fragment to yield CH2N and CH2O.

Keywords: [N(CH2)3]–, [ON(CH2)2]–, neutralisation rearrangement, energised N(CH23 and [ON(CH2)2], ring closure, fragmentation

Full-text article (1761 kB) (subscribers only)

Buy article on-line for £20 (get immediate access)

Alerting Service

 RSS Feed

Permalink: http://dx.doi.org/10.1255/ejms.952
QR Code (what is this?):

Alerting Services

Our Table of Contents Alerting Service will keep you up-to-date with the latest research published in our journals.

You can also follow our journals on Twitter or subscribe to their RSS feeds.  Follow us on Twitter and Subscribe to our RSS Feeds

Sign Up Now

Subscriptions

Discover the benefits of subscribing to our periodicals

  • Quality Science
  • Fair Pricing
  • Important Research
  • Flexible Subscriptions

Subscribe Today

Sample Copy of EJMS