Reactivity Trends of Lewis Acidic Sites in Methylaluminoxane and Some of Its Modifications

The established model cluster (AlOMe)16(AlMe3)6 for methylaluminoxane (MAO) cocatalyst has been studied by density functional theory, aiming to rationalize the different behaviors of unmodified MAO and TMA-depleted MAO/BHT (TMA = trimethylaluminum; BHT = 2,6-di-tert-butyl-4-methylphenol), highlighted in previous experimental studies. The tendency of the three model Lewis acidic sites A–C to release neutral Al fragments (i.e., AlMe2R; R = Me or bht) or transient aluminum cations (i.e., [AlMeR]+) has been investigated both in the absence and in the presence of neutral N-donors. Sites C are most likely responsible for the activation capabilities of TMA-rich MAO, but TMA depletion destabilizes them, possibly inducing structural rearrangements. The remaining sites A and B, albeit of lower Lewis acidity, should be still able to release cationic Al fragments when TMA-depleted modified MAOs are treated with N-donors (e.g. [AlMe­(bht)]+ from MAO/BHT). These findings provide tentative interpretations for earlier observations of donor-dependent ionization tendencies of MAO and MAO/BHT and how TMA depleted MAOs can still be potent activators.