Abstract
AbstractThe oxidation of methanol by oxygen, catalysed by copper‐phenanthroline complexes and promoted by the stable radical di‐tert‐butyl nitroxide, has been studied. The results are discussed in connection with the previously studied oxidation of methanol by copper‐phenanthroline complexes, catalysed by di‐tert‐butyl nitroxide, in the absence of oxygen.Similar systems in which ammonia was used instead of phenanthroline were also investigated, both under aerobic and anaerobic conditions. The results indicate that the promoter, di‐tert‐butyl nitroxide, is not involved in any reactions in which oxygen or radicals derived from oxygen participate, but that its sole function is to catalyse the reduction by methanol of cupric complex to the cuprous state. If oxygen is present, the cuprous ion then reacts with one mole of oxygen, yielding cupric complex and \documentclass{article}\pagestyle{empty}\begin{document}\[{\rm O}_{\rm 2}^{-\bullet}\]\end{document}, whereupon the \documentclass{article}\pagestyle{empty}\begin{document}\[{\rm O}_{\rm 2}^{-\bullet}\]\end{document} reacts with methanol coordinated to cupric ion, as in the aerobic oxidation of methanol catalysed by unpromoted copper‐phenanthroline complexes, described in the previous paper.Chain reactions propagated by hydroxymethyl radicals do not occur in the present reaction.
Published Version
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