Synthesis and characterisation of an enantiomerically pure scandium pentadienyl complex and its application in the polymerisation of rac -lactide.
Katharina MünsterJan RaederMarc D WalterPublished in: Dalton transactions (Cambridge, England : 2003) (2022)
The alkyl-functionalised scandium complex [(pdl*SiMe 2 N t Bu)Sc(thf)(CH 2 SiMe 3 )] (2) was synthesised in enantiomerically pure form and characterised by NMR spectroscopy and X-ray diffraction analysis. Complex 2 features a chiral constrained geometry ligand derived from the natural compound (1 R )-(-)-myrtenal, in which the pentadienyl (pdl*) fragment coordinates in η 3 :η 2 -allyl-en fashion to the scandium atom. Compound 2 catalyses the polymerisation of rac -lactide at 30 °C and 50 °C yielding amorphous poly(lactide) with slightly heterotactic enchainment ( P m = 0.36 and 0.37). In agreement with the data obtained from GPC and DSC measurements, a chain-end control mechanism is proposed with fast chain propagation relative to the initiation, which leads to broad molecular weight distributions ( Đ ≈ 1.80) and higher than expected molecular weights. Furthermore, chain transfer processes are observed, but only small amounts of transesterification and racemisation occur. Kinetic studies reveal a second-order dependence in rac -lactide (monomer) concentration and a first-order dependence in the concentration of catalyst 2.
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