title: Study of ligand substituent effects on the rate and stereoselectivity of lactide polymerization using aluminum salen-type initiators.
abstract: A series of aluminum salen-type complexes [where salen is N,N'-bis(salicylaldimine)-1,2-ethylenediamine] bearing ligands that differ in their steric and electronic properties have been synthesized and investigated for the polymerization of rac-lactide. X-ray crystal structures on key precatalysts reveal metal coordination geometries intermediate between trigonal bipyramidal and square-based pyramidal. Both the phenoxy substituents and the backbone linker have a significant influence over the polymerization. Electron-withdrawing groups attached to the phenoxy donor generally gave an increased polymerization rate, whereas large ortho substituents generally slowed down the polymerization. The vast majority of the initiators afforded polylactide with an isotactic bias; only one exhibited a bias toward heteroselectivity. Isoselectivity generally increases with increased flexibility of the backbone linker, which is presumed to be better able to accommodate any potential steric clashes between the propagating polymer chain, the inserting monomer unit, and the substituents on the phenoxy donor.
authors.affiliation: Department of Chemistry, Imperial College London, South Kensington Campus, London SW7 2AY, United Kingdom.
authors.forename: Pimpa
authors.initials: P
authors.lastname: Hormnirun
authors.forename: Edward L
authors.initials: EL
authors.lastname: Marshall
authors.forename: Vernon C
authors.initials: VC
authors.lastname: Gibson
authors.forename: Robert I
authors.initials: RI
authors.lastname: Pugh
authors.forename: Andrew J P
authors.initials: AJ
authors.lastname: White
mesh_terms: D000535:Aluminum / Q000737:chemistry*; D018360:Crystallography, X-Ray; D008024:Ligands; D015394:Molecular Structure; D011091:Polyesters / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D008024:Ligands; D011091:Polyesters; C033616:poly(lactide); D000535:Aluminum