Aminopiperidine based complexes for lactide polymerisation

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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 realized; 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 1H and 13C{1H} 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
Original languageEnglish
Pages (from-to)5374-5387
JournalDalton Transactions
Volume45
Issue number12
Early online date18 Feb 2016
DOIs
Publication statusPublished - 28 Mar 2016

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Polymerization
Ligands
Aluminum
Hafnium
Metals
X ray crystallography
Ring opening polymerization
dilactide
Isomers
Nuclear magnetic resonance spectroscopy

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Aminopiperidine based complexes for lactide polymerisation. / McKeown, P.; Davidson, M.G.; Lowe, J. P.; Mahon, M. F.; Thomas, L. H.; Woodman, T. J.; Jones, M. D.

In: Dalton Transactions , Vol. 45, No. 12, 28.03.2016, p. 5374-5387.

Research output: Contribution to journalArticle

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