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Article Abstract
A homoleptic calcium complex supported by a constrained reduced Schiff base ligand was synthesised and found to be highly active for the ring-opening polymerisation (ROP) of 100 equiv. lactide within 2 min at room temperature. However, the magnesium analogue has significantly lower reactivity. Single-crystal X-ray diffraction revealed a 6-coordinate metal environment for both complexes. Density functional theory (DFT) calculations showed that the calcium complex can asccommodate up to 7-coordination, thereby facilitating polymerisation without detachment of the dimethylamino sidearm, unlike in the magnesium complex. The participation of the phenoxy group and secondary amine (N-H) were observed to facilitate polymerisation hydrogen bonding.
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