Heterobimetallic aluminate derivatives with bulky phenoxide ligands: a catalyst for selective vinyl polymerization

New aluminium-alkali metal heterometallic compounds using the bulky ligand OAr = 2,6-bis(diphenylmethyl)-4- tert -butylphenoxide have been synthesized and characterized. The species obtained, [MAlMe 3 (OAr)] (M = Li( 2a ), Na( 2b ), K( 2c )) and [MAlMe 2 (OAr) 2 ] (M = Li( 3a ), Na( 3b ), K( 3c )), include some of the few heterobimetallic examples of aluminate complexes with O-donor ligands described so far. Their activity in polymerization towards a difunctional monomer, such as Glycidyl Methacrylate (GMA), was evaluated. The compounds were revealed to be able to polymerize the acrylate groups via vinyl polymerization. Interestingly, the homometallic counterparts [AlXMe(OAr)] (X = Cl, Me), previously described by us, are very active in ROP processes of GMA. The combined polymerization process using both catalysts has also been explored to obtain a polymeric material with an exciting macromolecular architecture. New aluminates as active catalysts for vinyl polymerization are described, as well as a strategy to crosslinked polymers from GMA in a controlled fashion.