Sittichoke TabthongTanin NanokPalangpon KongsaereeSamran PrabpaiPimpa HormnirunKasetsart UniversityMahidol University2018-11-092018-11-092014-01-21Dalton Transactions. Vol.43, No.3 (2014), 1348-135914779234147792262-s2.0-84890503394https://repository.li.mahidol.ac.th/handle/20.500.14594/33637Two series of aluminum alkyl complexes supported by pyrrolylaldiminate ligands, LAlMe2(1a-7a) and L2AlMe (1b-7b), were successfully synthesized and characterized by NMR spectroscopy and elemental analysis. Reactions of trimethylaluminum with the corresponding pyrrolylaldiminate ligands in the molar ratios of 1:1 and 1:2 yielded dimethylaluminum pyrrolylaldiminates (1a-7a) and monomethylaluminum pyrrolylaldiminates (1b-7b), respectively, in good yields. The structure of 3b, determined by single-crystal X-ray diffraction, displayed a distorted trigonal bipyramidal geometry with the τ value of 0.65. Upon addition of 1 equivalent of benzyl alcohol, all complexes promoted the living ring-opening polymerization of rac-lactide with a good control over molecular weights and polydispersities. Complexes 6a and 7a were found to efficiently mediate the immortal polymerization in the presence of excess equivalents of benzyl alcohol (up to 5 equivalents), as evidenced by the narrow PDI values and the good agreement between the experimental Mnvalues and monomer/benzyl alcohol ratios. The steric and electronic effects of the imine nitrogen substituents had a strong influence on the polymerization activities both in catalytic activity and polymer microstructure. The catalytic activity decreased as follows: 4-Me-C6H4(3) > C6H5(1) ≈ 4-F-C6H4(2) ≈ 2-Me-C6H4(5) > 4-OMe-C6H4(4) ≫ 2-tBu-C6H4(6) > adamantyl (7). In comparison, the catalytic activity of the monomethylaluminum complex is slightly higher than that of the dimethylaluminum counterpart. The polymerization of rac-lactide by 6b yielded heterotactically enriched polylactide (Pr= 0.60) whereas the isotactic-enriched polymer (Pm= 0.74) was obtained from 7b. © The Royal Society of Chemistry 2014.Mahidol UniversityChemistryMonomethylaluminum and dimethylaluminum pyrrolylaldiminates for the ring-opening polymerization of rac-lactide: Effects of ligand structure and coordination geometryArticleSCOPUS10.1039/c3dt52455h