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 +20 °C) using 13C nuclear magnetic resonance spectroscopy. These experiments were made possible by the utilisation of 13C doubly labelled oxalyl chloride, which was reacted with anhydrous hydrogen peroxide in dry tetrahydrofuran. Ab initio quantum calculations were also performed to estimate the 13C 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.