Abstract
The composition of methylalumoxane (MAO) and its interaction with trimethylaluminum (TMA) have been investigated by a combination of chemical, spectroscopic, neutron scattering, and computational methods. The interactions of MAO with donor molecules such as THF, pyridine, and PPh3 as a means of quantifying the content of “free” and “bound” TMA have been evaluated, as well as the ability of MAO to produce [Me2AlL2]+ cations, a measure of the electrophilic component likely to be involved in the activation of single-site catalysts. THF, pyridine, and diphenylphosphinopropane (dppp) give the corresponding TMA–donor ligand complexes accompanied by the formation of [Me2AlL2]+ cations. The results suggest that MAO contains not only Lewis acid sites but also structures capable of acting as sources of [AlMe2]+ cations. Another unique, but still unresolved, structural aspect of MAO is the nature of “bound” and “free” TMA. The addition of the donors OPPh3, PMe3, and PCy3 leads to the precipitation of polymeric MAO a...
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