Oxidation of Methylalumoxane Oligomers

The anions formed from methylalumoxane (MAO) and suitable donors (e.g. octamethyltrisiloxane) are amenable to mass spectrometric (MS) analysis. Their composition as deduced from this data allows direct insight into the chemical transformations of their neutral precursors. One such process is oxidation, which is well-known to be facile for MAO without any clear idea of what actually occurs at a molecular level. Addition of O₂ to MAO results in immediate gelation, but MS analysis reveals no corresponding change to the composition of the principal oligomeric anions. A slow (hours) reaction does occur that involves net incorporation of Me₂ AlOMe into the oligomeric anions, and the identities of the OMe-containing anions were confirmed by ¹ H NMR spectroscopy, MS/MS analysis, and addition of an authentic sample of Me₂ AlOMe to MAO. The result tallies with the fact that addition of O₂ to MAO produces Me₂ AlOMe from free Me₃ Al which eventually leads to formation of oxidized MAO oligomers and changes in ion abundance. Aging of the oxygenated MAO results in further growth of the oligomers similar to that of the non-oxidized species. Mass spectrometric analysis therefore reveals useful insights into the environmental history of a given MAO batch.