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

journal contribution
posted on 2008-05-05, 00:00 authored by S Tonkin, Richard Bos, Gail Dyson, Kieran LimKieran Lim, R Russell, S Watson, Christopher Hindson, Neil BarnettNeil Barnett
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.

History

Journal

Analytica chimica acta

Volume

614

Issue

2

Pagination

173 - 181

Publisher

Elsevier BV

Location

Amsterdam, The Netherlands

ISSN

0003-2670

eISSN

1873-4324

Language

eng

Publication classification

C1 Refereed article in a scholarly journal

Copyright notice

2008, Elsevier B.V.