Macromolecules · 2007 · 138 citations · 51 references
Materials ScienceInorganic ChemistryStructural CharacterizationEngineeringMacromolecular EngineeringCoordination ComplexRing-opening PolymerizationMagnesium ComplexesMagnesium Ketiminate ComplexesMolecular ComplexCoordination PolymerChemistryBiomolecular EngineeringDimeric SpeciesPolymer ReactionInorganic SynthesisPolymer ChemistryPolymer Synthesis
A series of dinuclear magnesium complexes of the type [LMg(μ-OBn)]2 (where L = NNO-tridentate ketiminate ligand) have been prepared. Their activities toward the ring-opening polymerization of l-lactide have been investigated. Experimental results indicate that the reactivity of [LMg(μ -OBn)]2 is dramatically affected by the steric and electronic effect of the substituents on the ketiminate ligand. On the basis of the melting point depression and variable-temperature 1H NMR studies, it is believed that these magnesium complexes exist as an equilibrium between a monomeric and a dimeric species in solution in which the monomeric species is the most active species during polymerization. The polymerization probably proceeds with the coordination of the lactide to the monomeric species giving a five-coordinated magnesium complex as an intermediate.
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