Studies on the mechanism of the peroxyoxalate chemiluminescence reaction : part 2, further identification of intermediates using 2D EXSY 13C nuclear magnetic resonance spectroscopy

Tonkin, Sarah A., Bos, Richard, Dyson, Gail A., Lim, Kieran F., Russell, Richard A., Watson, Simon P., Hindson, Christopher M. and Barnett, Neil W. 2008, Studies on the mechanism of the peroxyoxalate chemiluminescence reaction : part 2, further identification of intermediates using 2D EXSY 13C nuclear magnetic resonance spectroscopy, Analytica chimica acta, vol. 614, no. 2, pp. 173-181.

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Title Studies on the mechanism of the peroxyoxalate chemiluminescence reaction : part 2, further identification of intermediates using 2D EXSY 13C nuclear magnetic resonance spectroscopy
Formatted title Studies on the mechanism of the peroxyoxalate chemiluminescence reaction : part 2, further identification of intermediates using 2D EXSY 13C nuclear magnetic resonance spectroscopy
Author(s) Tonkin, Sarah A.
Bos, Richard
Dyson, Gail A.
Lim, Kieran F.
Russell, Richard A.
Watson, Simon P.
Hindson, Christopher M.
Barnett, Neil W.
Journal name Analytica chimica acta
Volume number 614
Issue number 2
Start page 173
End page 181
Total pages 9
Publisher Elsevier BV
Place of publication Amsterdam, The Netherlands
Publication date 2008-05-05
ISSN 0003-2670
1873-4324
Keyword(s) peroxyoxalate chemiluminescence
mechanism
key intermediates
2D EXSY 13C nuclear magnetic resonance spectroscopy
Summary 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 13C 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. 13C 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.
Language eng
Field of Research 030601 Catalysis and Mechanisms of Reactions
Socio Economic Objective 970103 Expanding Knowledge in the Chemical Sciences
HERDC Research category C1 Refereed article in a scholarly journal
HERDC collection year 2008
Copyright notice ©2008, Elsevier B.V.
Persistent URL http://hdl.handle.net/10536/DRO/DU:30017269

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