Fragmentations and reactions of some isotopically labelled dimethyl methylphosphono and trimethyl phosphoro thiolates and thionates studied by Electrospray Ionisation/Ion Trap Mass Spectrometry

Francesco Ferrante, Barr, Bell, Watts, Timperley, Mundy, Waters, Gianfranco La Manna

Research output: Contribution to journalArticlepeer-review

11 Citations (Scopus)

Abstract

In this paper, studies on electrospray ionisation ion trap mass spectrometry of organophosphates are extended to a series of dimethyl methylphosphono and trimethyl phosphoro thionates and thiolates and some deuterated isotopomers. Of particular, interest is the comparison of the collision-induced fragmentation of ions from these compounds with those of the non-sulphur containing analogues reported previously. The thiono and thiolo isomeric structures of the sulphur containing ions analogous to I and II (see below) have very similar energies and undergo a ready interconversion. In the case of the phosphono compounds, the electronic structure calculations show that the methyl migration implicit in thiono-thiolo interconversion occurs directly and although methyl migration from P to the phosphonyl O or phosphonothionyl S can occur, the transition state (TS) energies are somewhat higher and, in the case of the migration to O, too high to take part in any of the subsequent collision induced fragmentations. With one exception, the mechanisms proposed for some of these fragmentations are supported by electronic structure calculations at the DFT-B3LYP level. © 2005 Elsevier B.V. All rights reserved
Original languageEnglish
Pages (from-to)29-40
Number of pages12
JournalInternational Journal of Mass Spectrometry
Volume244
Publication statusPublished - 2005

All Science Journal Classification (ASJC) codes

  • Instrumentation
  • Condensed Matter Physics
  • Spectroscopy
  • Physical and Theoretical Chemistry

Fingerprint Dive into the research topics of 'Fragmentations and reactions of some isotopically labelled dimethyl methylphosphono and trimethyl phosphoro thiolates and thionates studied by Electrospray Ionisation/Ion Trap Mass Spectrometry'. Together they form a unique fingerprint.

Cite this