Abstract: | The solution structure of AlMe2F and its reactivity with a prototypical ansa‐metallocene have been investigated by advanced NMR techniques, in an attempt to indirectly shed some light on the structure and working principles of methylalumoxane (MAO) mixtures in olefin polymerization. In solution, AlMe2F gives rise to a complex equilibrium of oligomeric species, including a heterocubane (Me2Al)4F4] tetramer, resembling the behavior of MAO. This complex mixture reacts with (ETH)ZrMe2 (ETH=rac ‐ethylenebis(4,5,6,7‐tetrahydro‐1‐indenyl)]) to afford (ETH)ZrMeδ+(μ‐F)(AlMe2F)nAlMe3δ−] inner‐sphere ion pairs through successive insertions/deinsertions of AlMe2F units into the Zr⋅⋅⋅(μ‐F) bond. |