NacNac-zinc-pyridonate mediated ε-caprolactone ROP

• Published in: Dalton transactions : an international journal of inorganic chemistry Vol. 52; no. 47; pp. 17767 - 17775
• Main Authors: Hughes, Jack W J, Babula, Dawid J, Stowers-Veitch, Findlay, Yuan, Kang, Uzelac, Marina, Nichol, Gary S, Ingleson, Michael J, Garden, Jennifer A
• Format: Journal Article
• Language: English
• Published: England Royal Society of Chemistry 05.12.2023; The Royal Society of Chemistry
• Subjects: Catalytic activity; Catalytic converters; Chemical synthesis; Chemistry; Crystallization; Dipping; Initiators; Mass spectrometry; NMR spectroscopy; Ring opening polymerization; Zinc compounds
• ISSN: 1477-9226; 1477-9234; 1477-9234
• DOI: 10.1039/d3dt03344a

Herein we report the synthesis, isolation and polymerisation activity of two new zinc compounds based on a 2,6-diisopropylphenyl (Dipp) β-diiminate (NacNac) ligand framework with zinc also ligated by an amidate (2-pyridonate or 6-methyl-2-pyridonate) unit. The compounds crystallised as either monomeric (6-Me-2-pyridonate derivative) or dimeric (2-pyridonate) species, although both were found to be monomeric in solution H DOSY NMR spectroscopy, which was supported by DFT calculations. These observations suggest that both complexes initiate ring-opening polymerisation (ROP) through a single-site monometallic mechanism. High molecular weight poly ε-caprolactone (PCL) was achieved exogenous initiator-free ROP conditions with both catalysts. An increase in the 2-pyridonate initiator steric bulk (6-Me- 6-H-) resulted in an improved catalytic activity, facilitating complete monomer conversion within 1 h at 60 °C. Pyridonate end-groups were observed by MALDI-ToF mass spectrometry, contrasting with previous observations for NacNac-Zn acetate complexes (where no acetate end groups are observed), instead this more closely resembles the reactivity of NacNac-Zn alkoxide complexes in ROP (where RO end groups are observed). Additional major signals in the MALDI-ToF spectra were consistent with cyclic PCL species, which are attributed to back-biting ring-closing termination steps occuring in a process facilitated by the pyridonate unit being an effective leaving group. To the best of our knowledge, these complexes represent the first examples of pyridonate, and indeed amidate, initated ROP.