Ring-opening polymerisation of l- and rac-lactide using group 4 permethylpentalene aryloxides and alkoxides

A new family of group 4 permethylpentalene (C₈Me₆^2-; Pn*) aryloxide and alkoxide complexes have been synthesised and fully characterised by multinuclear NMR spectroscopy and single-crystal X-ray diffraction; (η⁸-C₈Me₆)Zr(OR)₂ (R = ^tBu (1), 2,6-Me-C₆H₃ (2), 2,6-ⁱPr-C₆H₃ (3) and 4-OMe-C₆H₄ (4)), (η⁸-C₈Me₆)Zr (OR) (R = 2,6-^tBu-C₆H₃ (5) and 2,6-^tBu-4-Me-C₆H₂ (6)), (η⁸-C₈Me₆)ZrCp(OR) (R = ^tBu (7), 2,6-Me-C₆H₃ (8) and 2,6-ⁱPr-C₆H₃ (9)), (η⁸-C₈Me₆)TiCp(O-2,6-Me-C₆H₃) (10) and (η⁸-C₈Me₆)ZrCp^Me(OR) (R = 2,6-Me-C₆H₃ (11), 2,6-ⁱPr-C₆H₃ (12) and 2,4-^tBu-C₆H₃ (13)). 2, 3, 6, 7, 9, 10 and 12 were studied as initiators for the ring-opening polymerisation (ROP) of l-lactide, and 2, 3, 6, 7 and 10 were studied as initiators for the ROP of rac-lactide. 3 was found to be the most active initiator for the ROP of l-lactide (k_obs = 0.35 h^-1) and 2 for the ROP of rac-lactide (k_obs = 0.21 h^-1). These initiators produced isotactic PLA for the ROP of l-lactide and moderately heterotactic enriched (maximum P_r of 0.69) or atactic PLA for the ROP of rac-lactide with polymer chains consisting of polylactic acid repeat units with -OR and -OH end groups.