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Updated: Mar 30, 2026

Controlled Photoredox Ring-Opening Polymerization of O-Carboxyanhydrides Mediated by Ni/Zn Complexes
Published on: November 21, 2017
Ring-opening polymerization of rac-lactide mediated by tetrametallic lithium and sodium diamino-bis(phenolate)
Dalal Alhashmialameer1, Nduka Ikpo1, Julie Collins2
1Department of Chemistry, Memorial University of Newfoundland, St. John's, Newfoundland, Canada A1B 3X7. fkerton@mun.ca.
Abstract:
Lithium and sodium compounds supported by tetradentate amino-bis(phenolato) ligands, [Li2(N2O2(BuBuPip))] (1), [Na2(N2O2(BuBuPip))] (2) (where [N2O2(BuBuPip)] = 2,2'-N,N'-homopiperazinyl-bis(2-methylene-4,6-tert-butylphenol), and [Li2(N2O2(BuMePip))] (3), [Na2(N2O2(BuMePip))] (4) (where [N2O2(BuMePip)] = 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, (7)Li NMR experiments show growth of a new resonance when 1 is mixed with 1 equiv. LA and (1)H NMR data suggests formation of a Li-alkoxide species upon reaction of 1 with BnOH.
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