Issue 6, 2004
From the journal:

Physical Chemistry Chemical Physics

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

A. J. Bell,a   A. Citra,b   J. M. Dyke,b   F. Ferrante,c   L. Gagliardic  and  P. Watts*a  

* Corresponding authors

a Dstl, Porton Down, Salisbury, Wiltshire, UK
E-mail: pwatts.rsg@ukgateway.net

b Department of Chemistry, Southampton University, Southampton, UK

c Dipartimento di Chimica Fisica “F. Accascina”, Università degli Studi di Palermo, 90128 Palermo, Italy

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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Article information

DOI
https://doi.org/10.1039/B315944B
Article type
Paper
Submitted
09 Dec 2003
Accepted
22 Jan 2004
First published
17 Feb 2004

Phys. Chem. Chem. Phys., 2004,6, 1213-1218

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

A. J. Bell, A. Citra, J. M. Dyke, F. Ferrante, L. Gagliardi and P. Watts, Phys. Chem. Chem. Phys., 2004, 6, 1213 DOI: 10.1039/B315944B

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