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An ab initio and DFT study of the fragmentation and isomerisation of MeP(O)(OMe)(+)

An ab initio and DFT study of the fragmentation and isomerisation of MeP(O)(OMe)(+)
An ab initio and DFT study of the fragmentation and isomerisation of MeP(O)(OMe)(+)
The fragmentation behaviour of the ion MeP(O)OMe+ has been investigated using quantum mechanical calculations at the B3LYP and MP2 levels to support experiments made with an Ion Trap Mass Spectrometer. Two mechanisms for the loss of CH2O are found, one involving a 1,3-H migration to phosphorus and the other a 1,2-methyl migration to give P(OMe)(2)(+) followed by a 1,3-H migration. In each case an ion-dipole complex is formed that rapidly dissociates to yield CH2O. The relative importance of each route has been previously determined experimentally via isotopic labelling experiments, and the theoretical results are found to be consistent with these experimental results. The mechanisms suggested in the earlier work involving a 1,4 H migration to O are shown to be energetically unfavourable.
mass-spectrometry, ion-trap, ch3o-p=o-center-dot+, ionization
1463-9076
1213-1218
Bell, A J.
e17a1725-7dfc-49e5-9484-cb71014b792a
Citra, A.
889aafbd-b6e0-4386-b3bc-7ad51429c21b
Dyke, J.M.
46393b45-6694-46f3-af20-d7369d26199f
Ferrante, F.
cff3f6ec-876e-45c4-bb06-ac2734fdd3ee
Gagliardi, L.
7289d411-f5b8-4b27-ae02-4eac1ee375b3
Watts, P.
98213bc9-aedd-4341-aab0-cfb019b73aeb
Bell, A J.
e17a1725-7dfc-49e5-9484-cb71014b792a
Citra, A.
889aafbd-b6e0-4386-b3bc-7ad51429c21b
Dyke, J.M.
46393b45-6694-46f3-af20-d7369d26199f
Ferrante, F.
cff3f6ec-876e-45c4-bb06-ac2734fdd3ee
Gagliardi, L.
7289d411-f5b8-4b27-ae02-4eac1ee375b3
Watts, P.
98213bc9-aedd-4341-aab0-cfb019b73aeb

Bell, A J., Citra, A., Dyke, J.M., Ferrante, F., Gagliardi, L. and Watts, P. (2004) An ab initio and DFT study of the fragmentation and isomerisation of MeP(O)(OMe)(+). Physical Chemistry Chemical Physics, 6 (6), 1213-1218. (doi:10.1039/b315944b).

Record type: Article

Abstract

The fragmentation behaviour of the ion MeP(O)OMe+ has been investigated using quantum mechanical calculations at the B3LYP and MP2 levels to support experiments made with an Ion Trap Mass Spectrometer. Two mechanisms for the loss of CH2O are found, one involving a 1,3-H migration to phosphorus and the other a 1,2-methyl migration to give P(OMe)(2)(+) followed by a 1,3-H migration. In each case an ion-dipole complex is formed that rapidly dissociates to yield CH2O. The relative importance of each route has been previously determined experimentally via isotopic labelling experiments, and the theoretical results are found to be consistent with these experimental results. The mechanisms suggested in the earlier work involving a 1,4 H migration to O are shown to be energetically unfavourable.

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More information

Published date: 21 March 2004
Keywords: mass-spectrometry, ion-trap, ch3o-p=o-center-dot+, ionization

Identifiers

Local EPrints ID: 20129
URI: http://eprints.soton.ac.uk/id/eprint/20129
ISSN: 1463-9076
PURE UUID: 408f2eff-5b3e-49e5-b94e-ec2e48b6b836
ORCID for J.M. Dyke: ORCID iD orcid.org/0000-0002-9808-303X

Catalogue record

Date deposited: 23 Feb 2006
Last modified: 20 Jul 2019 01:27

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Contributors

Author: A J. Bell
Author: A. Citra
Author: J.M. Dyke ORCID iD
Author: F. Ferrante
Author: L. Gagliardi
Author: P. Watts

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