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• W4306174849 abstract "The replacement of the imine functionality in the ubiquitous phenoxy-imine (FI) ligands by a more robust and donor N,N,N′-trisubstituted amidine function was examined and gave rise to the synthesis of five new phenoxy-amidine (FA) ligands (L1–L5). The solid-state structure of four proligands has been determined by X-ray diffraction analysis and showed that the amidine moiety is in a trans-configuration. The reaction of the phenol-amidine proligands with AlMe3 afforded mononuclear (L1–L5)AlMe2 (1a–5a). A similar alkane elimination route was used from ZnEt2 and led to dinuclear [(L1–L5)ZnEt]2 complexes (1b–5b) or to homoleptic (L2/L4)2Zn complexes (2b′, 4b′) depending on the metal/ligand ratio used. The structure of these complexes has been determined by NMR spectroscopy (1H, 13C, HMBC, HSQC, DOSY, and NOESY experiments) and X-ray diffraction study for seven of them. The crystal structure of the Al complexes showed FA ligands coordinated in a chelate fashion via the O atom of the aryloxy group and the imino-N atom, indicating that the amidine function has undergone trans–cis isomerization upon coordination. A similar chelating coordination mode was observed for the FA ligands with Zn metal ions. These complexes were used as initiators for the ring-opening polymerization of rac-lactide. FA–Zn complexes gave the best performance, affording polylactic acid with a narrow molecular weight distribution and heterotactic bias (Pr up to 0.75). Remarkably, some of these complexes were able to tolerate the presence of a large amount of lactic acid to the point of using it as a co-initiator during the polymerization reaction." @default.
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• W4306174849 date "2022-10-14" @default.
• W4306174849 modified "2023-10-18" @default.
• W4306174849 title "Phenoxy-Amidine Ligands: Toward Lactic Acid-Tolerant Catalysts for Lactide Ring-Opening Polymerization" @default.
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• W4306174849 doi "https://doi.org/10.1021/acs.organomet.2c00343" @default.
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