Studies on the mechanism of the peroxyoxalate chemiluminescence reaction.: Part 1.: Confirmation of 1,2-dioxetanedione as an intermediate using 13C nuclear magnetic resonance spectroscopy

A simple model peroxyoxalate chemiluminescence system was monitored directly across a range of temperatures (from -80 to +20degreesC) using C-13 nuclear magnetic resonance spectroscopy. These experiments were made possible by the utilisation of C-13 doubly labelled oxalyl chloride, which was reacted with anhydrous hydrogen peroxide in dry tetrahydrofuran. Ab initio quantum calculations were also performed to estimate the C-13 nuclear magnetic resonance (NMR) shift of the most commonly postulated key intermediate 1,2-dioxetanedione and this data, in concert with the spectroscopic evidence, confirmed its presence during the reaction. (C) 2003 Elsevier B.V. All rights reserved.