Phenoxy-Amidine Ligands: Toward Lactic Acid-Tolerant Catalysts for Lactide Ring-Opening Polymerization

• Published in: Organometallics Vol. 41; no. 21; pp. 2920 - 2932
• Main Authors: Vaillant-Coindard, Valentin, Théron, Benjamin, Printz, Gaël, Chotard, Florian, Balan, Cédric, Rousselin, Yoann, Richard, Philippe, Tolbatov, Iogann, Fleurat-Lessard, Paul, Bodio, Ewen, Malacea-Kabbara, Raluca, Bayardon, Jérôme, Dagorne, Samuel, Le Gendre, Pierre
• Format: Journal Article
• Language: English
• Published: American Chemical Society 14-11-2022
• Subjects: Catalysis; Chemical Sciences; Coordination chemistry
• ISSN: 0276-7333; 1520-6041
• DOI: 10.1021/acs.organomet.2c00343

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.