title: Aminopiperidine based complexes for lactide polymerisation.
abstract: Herein we report the synthesis and characterisation of a series of salalen and salan ligands derived from 2-(aminomethyl)piperidine. Depending on the choice of starting salicylaldehyde, a bicyclic salan type ligand (1-3H2) or imino salalen type ligand (4-6H, 7-9H2) were prepared. The ligands were successfully complexed to group 4 metals and aluminium; with hafnium and zirconium octahedral complexes, M(1-3)2, were realised; whilst with aluminium tetrahedral and trigonal bipyramidal complexes, Al(1-9)Mex (x = 1,2), were isolated. The complexes have been characterised in solution via(1)H and (13)C{(1)H} NMR spectroscopy and in the solid state by X-ray crystallography. The group 4 complexes were observed to have a fac-fac arrangement of ligands and there were two isomers present when 3H2 was ligated. The imino aluminium complexes Al(7-9)Me were isolated as a mixture of diastereoisomers. The resultant complexes were trialed in the ring opening polymerisation of rac-lactide with both heterotactic and isotactic PLA being demonstrated. Tacticity was found to be dependent on the nature of the ligand and metal used; the M(1-3)2 complexes were generally found to have a heterotactic preference (Pr = 0.67-0.76) and the aluminium polymerisation outcome was dictated more by the steric influence of the ligand, particularly for Al(4/6)Me2/Al(7/9)Me.
authors.affiliation: Doctoral Training Centre in Sustainable Chemical Technologies, University of Bath, Bath BA2 7AY, UK and Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, UK. mj205@bath.ac.uk.
authors.forename: P
authors.initials: P
authors.lastname: McKeown
authors.affiliation: Doctoral Training Centre in Sustainable Chemical Technologies, University of Bath, Bath BA2 7AY, UK and Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, UK. mj205@bath.ac.uk.
authors.forename: M G
authors.initials: MG
authors.lastname: Davidson
authors.affiliation: Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, UK. mj205@bath.ac.uk.
authors.forename: J P
authors.initials: JP
authors.lastname: Lowe
authors.affiliation: Crystallography Centre, Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, UK. m.f.mahon@bath.ac.uk.
authors.forename: M F
authors.initials: MF
authors.lastname: Mahon
authors.affiliation: Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, UK. mj205@bath.ac.uk.
authors.forename: L H
authors.initials: LH
authors.lastname: Thomas
authors.affiliation: Doctoral Training Centre in Sustainable Chemical Technologies, University of Bath, Bath BA2 7AY, UK.
authors.forename: T J
authors.initials: TJ
authors.lastname: Woodman
authors.affiliation: Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, UK. mj205@bath.ac.uk.
authors.forename: M D
authors.initials: MD
authors.lastname: Jones