Ring-opening polymerization of rac-lactide mediated by tetrametallic lithium and sodium diamino-bis(phenolate) complexes

Kerton, Francesca M. and Alhashmialameer, Dalal and Ikpo, Nduka and Collins, Julie and Hattenhauer, Karen (2015) Ring-opening polymerization of rac-lactide mediated by tetrametallic lithium and sodium diamino-bis(phenolate) complexes. Dalton Transactions, 44 (46). pp. 20216-20231. ISSN 1477-9234

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Abstract

Lithium and sodium compounds supported by tetradentate amino-bis(phenolato) ligands, [Li2(N2O2BuBuPip)] (1), [Na2(N2O2BuBuPip)] (2) (where [N2O2BuBuPip] = 2,2′-N,N’-homopiperazinyl-bis(2-methylene-4,6-tert-butylphenol), and [Li2(N2O2BuMePip)] (3), [Na2(N2O2BuMePip)] (4) (where [N2O2BuMePip] = 2,2′-N,N’-homopiperazinyl-bis(2-methylene-4-methyl-6-tert-butylphenol) were synthesized and characterized by NMR spectroscopy and MALDI-TOF mass spectrometry. Variable temperature NMR experiments were performed to understand solution-phase dynamics. The solid-state structures of 1 and 4 were determined by X-ray diffraction and reveal tetrametallic species. PGSE NMR spectroscopic data suggests that 1 maintains its aggregated structure in CD2Cl2. The complexes exhibit good activity for controlled ring-opening polymerization of rac-lactide (LA) both solvent free and in solution to yield PLA with low dispersities. Stoichiometric reactions suggest that the formation of PLA may proceed by the typical coordination–insertion mechanism. For example, 7Li NMR experiments show growth of a new resonance when 1 is mixed with 1 equiv. LA and 1H NMR data suggests formation of a Li-alkoxide species upon reaction of 1 with BnOH.

Item Type: Article
URI: http://research.library.mun.ca/id/eprint/13368
Item ID: 13368
Department(s): Science, Faculty of > Chemistry
Date: 5 November 2015
Date Type: Publication
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