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Type: Journal article
Title: Studies on the mechanism of the peroxyoxalate chemiluminescence reaction - Part 2. Further identification of intermediates using 2D EXSY C-13 nuclear magnetic resonance spectroscopy
Author: Tonkin, S.
Bos, R.
Dyson, G.
Lim, K.
Russell, R.
Watson, S.
Hindson, C.
Barnett, N.
Citation: Analytica Chimica Acta, 2008; 614(2):173-181
Publisher: Elsevier Science BV
Issue Date: 2008
ISSN: 0003-2670
Statement of
Sarah A. Tonkin, Richard Bos, Gail A. Dyson, Kieran F. Lim, Richard A. Russell, Simon P. Watson, Christopher M. Hindson and Neil W. Barnett
Abstract: Further consideration has been given to the reaction pathway of a model peroxyoxalate chemiluminescence system. Again utilising doubly labelled oxalyl chloride and anhydrous hydrogen peroxide, 2D EXSY (13)C nuclear magnetic resonance (NMR) spectroscopy experiments allowed for the characterisation of unknown products and key intermediate species on the dark side of the peroxyoxalate chemiluminescence reaction. Exchange spectroscopy afforded elucidation of a scheme comprised of two distinct mechanistic pathways, one of which contributes to chemiluminescence. (13)C NMR experiments carried out at varied reagent molar ratios demonstrated that excess amounts of hydrogen peroxide favoured formation of 1,2-dioxetanedione: the intermediate that, upon thermolysis, has been long thought to interact with a fluorophore to produce light.
Keywords: Peroxyoxalate chemiluminescence; Mechanism; Key intermediates; 2D EXSY 13C nuclear magnetic resonance spectroscopy
Rights: © 2008 Published by Elsevier B.V.
RMID: 0020080712
DOI: 10.1016/j.aca.2008.03.009
Appears in Collections:Adelaide Graduate Centre publications

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