1. Phenoxyamidine Zn and Al Complexes: Synthesis, Characterization, and Use in the Ring-Opening Polymerization of Lactide
- Author
-
Pierre Le Gendre, Stefano Milione, Alfonso Grassi, Audrey Trommenschlager, Raluca Malacea-Kabbara, Quentin Bonnin, Rosita Lapenta, Hélène Cattey, Jérôme Bayardon, Philippe Richard, Cédric Balan, Samuel Dagorne, Florian Chotard, Anaëlle Bolley, Ewen Bodio, Institut de Chimie Moléculaire de l'Université de Bourgogne [Dijon] (ICMUB), Centre National de la Recherche Scientifique (CNRS)-Université de Bourgogne (UB)-Institut de Chimie du CNRS (INC), Journaliste, AFP, Institut de Chimie de Strasbourg, Centre National de la Recherche Scientifique (CNRS)-Université Louis Pasteur - Strasbourg I-Institut de Chimie du CNRS (INC), European Regional Development Fund, Université de Bourgogne, Ministère de l'Enseignement Supérieur et de la Recherche Scientifique, Centre National de la Recherche Scientifique, and Conseil régional de Bourgogne-Franche-Comté
- Subjects
STRUCTURAL-CHARACTERIZATION ,chemistry.chemical_element ,CATALYSTS ,Zinc ,010402 general chemistry ,LIGANDS SYNTHESIS ,01 natural sciences ,Ring-opening polymerization ,Coordination complex ,Catalysis ,Inorganic Chemistry ,chemistry.chemical_compound ,ZINC ,IMINE LIGANDS ,Group (periodic table) ,Polymer chemistry ,[CHIM.COOR]Chemical Sciences/Coordination chemistry ,Physical and Theoretical Chemistry ,Methylene ,CYCLIC ESTERS ,ALUMINUM COMPLEXES ,chemistry.chemical_classification ,EPSILON-CAPROLACTONE ,Lactide ,010405 organic chemistry ,Organic Chemistry ,GROUP-4 METAL-COMPLEXES ,[CHIM.CATA]Chemical Sciences/Catalysis ,Imine ligands ,0104 chemical sciences ,chemistry ,INITIATORS - Abstract
International audience; Herein we report the synthesis of new ditopic ligands, which consist of a phenoxy group and N,N,N'trisubstituted amidines linked by a methylene spacer (L1-L4). Their coordination chemistry has been studied/investigated with Zn(II) and Al(III). Alkane elimination route between the phenol-amidine proligands (L1H-L4H) and Et2Zn led to dinuclear complexes [(L1-L4)ZnEt]2 (1a-4a) in which the Zn centers are chelated by phenoxyamidine ligands and bridged through the oxygen atom of the phenoxy groups. Salt metathesis reaction between two equivalents of the sodium amidine phenate L1Na and ZnCl2 led to a bis-chelate chiral spiro-complex (L12Zn) 1a'. Analogous alkane elimination route between AlMe3 and the phenol-amidine proligands L1H-L4H allowed the preparation of the mononuclear complexes [(L1-L4)AlMe2] (1b-4b). The phenoxyamidine-Al and Zn complexes have been characterized by NMR spectroscopy, elemental analysis and/or high resolution ESI-MS. The solid state structures of the proligands [L1H2][Br] and L2H as well as of six complexes have been established by single crystal X-ray diffraction analysis. Fluxional properties of the proligands L1H-L2H and of the complexes 1a and 2b have been investigated by VT NMR experiments. In the presence of an alcohol source, complexes 1a-4a and 1b-4b were used as initiators for the controlled ring-opening polymerization (ROP) of rac-lactide to afford atactic polylactic acid (PLA).
- Published
- 2019