Reaction of R1R2CHN=CH(3,5-tBu2C6H2-OH-2) (R1 = R2 = Me L1H; R1 = Me, R2 = Ph L2H; R1 = R2 = Ph L3H) with slightly greater than one equivalent of R3 3Al (R3 = Me, Et) afforded the complexes [(L1–3)AlR3 2] (L1, R3 = Me 1, R3 = Et 2; L2, R3 = Me 3, R3 = Et 4; L3 R3 = Me 5, R3 = Et 6); complex 1 has been previously reported. Use of the N,O-ligand derived from 2,2?-diphenylglycine afforded either 5 or the byproduct [Ph2NCH2(3,5-tBu2C6H2-O-2)AlMe2] (7). The known Schiff base complex [2-Ph2PC6H4CH2(3,5-tBu2C6H2-O-2)AlMe2] (8) and the product of the reaction of 2-diphenylphosphinoaniline 1-NH2,2- PPh2C6H4 with Me3Al, namely {Ph2PC6H4N[(Me2Al)2?-Me]- (?-Me2Al)} (9), were also isolated. For structural and catalytic comparisons, complexes resulting from the interaction of Me3Al with diphenylamine (or benzhydrylamine), namely {Ph2N[(Me2Al)2?-Me]} (10) and [Ph2CHNH(?-Me2Al)]2·MeCN (11), were prepared. The molecular structures of the Schiff proligands derived from Ph2CHNH2 and 2,2?-Ph2C(CO2H)(NH2), together with those of complexes 5, 7 and 9–11·MeCN were determined; 5 contains a chelating imino/phenoxide ligand, whereas 7 contains the imino function outside of the metallocyclic ring. Complex 9 contains three nitrogen-bound Al centres, two of which are linked by a methyl bridge, whilst the third bridges the N and P centres. In 10, the structure resembles 9 with a bridging methyl group, whereas the introduction of the extra carbon in 11 results in the formation of a dimer. All complexes have been screened for their ability to promote the ring-opening polymerization (ROP) ?-caprolactone, ?-valerolactone or rac-lactide, in the presence of benzyl alcohol, with or without solvent present. Reasonable conversions were achievable at room temperature for ?-caprolactone when using complexes 7, 9 and 12, whilst at higher temperatures (80– 110 °C), all complexes produced good (> 65 %) to quantitative conversions over periods as short as 3 min, albeit with poor control. In the absence of solvent, conversions were nearly quantitative at 80 °C in 5 min with better agreement between observed and calculated molecular weight (Mn). For rac-lactide, conversions were typically in the range 71–86 % at 110 °C in
12 h, with poor control affording atactic polylactide (PLA), whilst for ?-valerolactone more forcing conditions (12–24 h at 110 °C) were required for high conversion. Co-polymerization of ?-caprolactone with rac-lactide afforded co-polymers with appreciable lactide content (35–62.5 %); the reverse addition was ineffective, affording only (polycaprolactone) PCL.