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

Risultato della ricerca: Article

11 Citazioni (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
Lingua originaleEnglish
pagine (da-a)29-40
Numero di pagine12
RivistaInternational Journal of Mass Spectrometry
Volume244
Stato di pubblicazionePublished - 2005

Fingerprint

Electrospray ionization
Mass spectrometry
fragmentation
mass spectroscopy
Ions
ionization
Electronic structure
electronic structure
collisions
Organophosphates
Electron transitions
Sulfur
Discrete Fourier transforms
Electron energy levels
ions
sulfur
analogs
energy

All Science Journal Classification (ASJC) codes

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

Cita questo

@article{e5c86820eb464ff8a84f67a8183aa970,
title = "Fragmentations and reactions of some isotopically labelled dimethyl methylphosphono and trimethyl phosphoro thiolates and thionates studied by Electrospray Ionisation/Ion Trap Mass Spectrometry",
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. {\circledC} 2005 Elsevier B.V. All rights reserved",
author = "Francesco Ferrante and Barr and Bell and Watts and Timperley and Mundy and Waters and {La Manna}, Gianfranco",
year = "2005",
language = "English",
volume = "244",
pages = "29--40",
journal = "International Journal of Mass Spectrometry",
issn = "1387-3806",
publisher = "Elsevier",

}

TY - JOUR

T1 - Fragmentations and reactions of some isotopically labelled dimethyl methylphosphono and trimethyl phosphoro thiolates and thionates studied by Electrospray Ionisation/Ion Trap Mass Spectrometry

AU - Ferrante, Francesco

AU - Barr, null

AU - Bell, null

AU - Watts, null

AU - Timperley, null

AU - Mundy, null

AU - Waters, null

AU - La Manna, Gianfranco

PY - 2005

Y1 - 2005

N2 - 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

AB - 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

UR - http://hdl.handle.net/10447/15538

M3 - Article

VL - 244

SP - 29

EP - 40

JO - International Journal of Mass Spectrometry

JF - International Journal of Mass Spectrometry

SN - 1387-3806

ER -