Well-defined Ti₄ pre-catalysts for the ring-opening polymerisation of lactide

The synthesis and full characterisation of four discrete tetrametallic titanium complexes is reported. These well-defined compounds are isostructural in the solid state and share the same general formula: Ti₄(μ-O)₂L₄ (L = 1, 2, 3 or 4). Using a combination of NMR techniques the complexes are found to be stable in solution, even at elevated temperatures. Further studies show that the carboxylate moieties of the supporting amine bis(phenolate) ligands can be displaced by a more strongly coordinating solvent. This reversible process causes the coordinatively saturated Ti₄(μ-O)₂L₄ complexes to separate into two Ti₂(μ-O)L₂ subunits which we envisaged would be catalytically active. Proof-of-concept experiments establish that all four of these complexes display catalytic activity in the ring-opening polymerisation of rac-lactide. These aggregates can therefore be viewed as air and moisture stable pre-catalysts for a range of reactions.