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Fragmentations and reactions of some isotopically labelled dimethyl methyl phosphono and trimethyl phosphoro thiolates and thionates studied by electrospray ionisation ion trap mass spectrometry

Fragmentations and reactions of some isotopically labelled dimethyl methyl phosphono and trimethyl phosphoro thiolates and thionates studied by electrospray ionisation ion trap mass spectrometry
Fragmentations and reactions of some isotopically labelled dimethyl methyl phosphono and trimethyl phosphoro thiolates and thionates studied by electrospray ionisation ion trap mass spectrometry
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.
mass spectrometry, electrospray, ion trap, organophosphates, thiono-thiolo rearrangement, organophosphorus compounds, alkyl iodides, isomerization, esters, rearrangements, reactivity, impact
1387-3806
29-40
Barr, J.D.
c54182e7-c4d4-4161-a42f-1898fd5f8aff
Bell, A.J.
a3daf8c9-3047-4f42-8038-b839ff6ec575
Ferrante, F.
cff3f6ec-876e-45c4-bb06-ac2734fdd3ee
La Manna, G.
af3aa5d3-5f1c-4fce-aad0-905cd971713c
Mundy, J.L.
2756b644-e38a-4b35-a8e8-2ba8fd4e180c
Timperley, C.M.
edc8d723-7947-45ad-9de8-65474e0f4d15
Waters, M.J.
bd9823a5-3220-460b-b5cb-91fb904512fb
Watts, P.
98213bc9-aedd-4341-aab0-cfb019b73aeb
Barr, J.D.
c54182e7-c4d4-4161-a42f-1898fd5f8aff
Bell, A.J.
a3daf8c9-3047-4f42-8038-b839ff6ec575
Ferrante, F.
cff3f6ec-876e-45c4-bb06-ac2734fdd3ee
La Manna, G.
af3aa5d3-5f1c-4fce-aad0-905cd971713c
Mundy, J.L.
2756b644-e38a-4b35-a8e8-2ba8fd4e180c
Timperley, C.M.
edc8d723-7947-45ad-9de8-65474e0f4d15
Waters, M.J.
bd9823a5-3220-460b-b5cb-91fb904512fb
Watts, P.
98213bc9-aedd-4341-aab0-cfb019b73aeb

Barr, J.D., Bell, A.J., Ferrante, F., La Manna, G., Mundy, J.L., Timperley, C.M., Waters, M.J. and Watts, P. (2005) Fragmentations and reactions of some isotopically labelled dimethyl methyl phosphono and trimethyl phosphoro thiolates and thionates studied by electrospray ionisation ion trap mass spectrometry. International Journal of Mass Spectrometry, 244 (1), 29-40. (doi:10.1016/j.ijms.2005.04.004).

Record type: Article

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.

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More information

Published date: 15 June 2005
Keywords: mass spectrometry, electrospray, ion trap, organophosphates, thiono-thiolo rearrangement, organophosphorus compounds, alkyl iodides, isomerization, esters, rearrangements, reactivity, impact

Identifiers

Local EPrints ID: 20709
URI: https://eprints.soton.ac.uk/id/eprint/20709
ISSN: 1387-3806
PURE UUID: 0c5a51e4-e938-43f5-a712-532e93b405ab

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Date deposited: 28 Feb 2006
Last modified: 17 Jul 2017 16:28

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Contributors

Author: J.D. Barr
Author: A.J. Bell
Author: F. Ferrante
Author: G. La Manna
Author: J.L. Mundy
Author: C.M. Timperley
Author: M.J. Waters
Author: P. Watts

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