Ionization of Cp₂ ZrMe₂ and Lewis Bases by Methylaluminoxane: Computational Insights

The interactions of the Lewis bases CO, octamethyltrisiloxane (OMTS) and 2,2'-bipyridine (bipy) with a sheet model for the principal activator (MeAlO)₁₆ (Me₃ Al)₆ (16,6) in hydrolytic methylaluminoxane (MAO) were investigated by DFT. These studies reveal that OMTS and bipy form adducts with Me₃ Al prior to methide abstraction by 16,6 to form the ion-pairs [Me₂ Al(κ² -L)][16,6] (5: L=OMTS, 6: L=bipy, [16,6]^- =[(MeAlO)₁₆ (Me₃ Al)₆ Me]^- ) while CO simply binds to a reactive edge site without ionization. The binding and activation of Cp₂ ZrMe₂ with 16,6 to form both neutral adducts 1 Cp₂ ZrMe₂ ⋅16,6 and contact ion-pairs 4 and 7, both with formula [Cp₂ ZrMe][μ-Me(MeAlO)₁₆ (Me₃ Al)₆ ], featuring terminal and chelated MAO-anions, respectively was studied by DFT. The displacement of the anion with either excess Cp₂ ZrMe₂ or Me₃ Al was also studied, forming outer-sphere ion-pairs [(Cp₂ ZrMe)₂ μ-Me][16,6] (2) and [Cp₂ Zr(μ-Me)₂ AlMe₂ ][16,6] (3). The theoretical NMR spectra of these species were compared to experimental spectra of MAO and Cp₂ ZrMe₂ and found to be in good agreement with the reported data and assignments. These studies confirm that 16,6 is a very suitable model for the activators present in MAO but highlight the difficulty in accurately calculating thermodynamic quantities for molecules in this size regime.