Aluminum Methyl and Chloro Complexes Bearing Monoanionic Aminephenolate Ligands: Synthesis, Characterization, and Use in Polymerizations

Kerton, Francesca M. and Ikpo, Nduka and Barbon, Stephanie M. and Drover, Marcus W. and Dawe, Louise N. (2012) Aluminum Methyl and Chloro Complexes Bearing Monoanionic Aminephenolate Ligands: Synthesis, Characterization, and Use in Polymerizations. Organometallics, 31 (23). pp. 8145-8158. ISSN 1520-6041

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A series of aluminum methyl and chloride complexes bearing 2(N-piperazinyl-N′-methyl)-2-methylene-4-R′-6-R-phenolate or 2(N-morpholinyl)-2-methylene-4-R′-6-R-phenolate ([ONER1,R2]-) {[R1 = tBu, R2 = Me, E = NMe (L1); R1= R2 = tBu, E = NMe (L2); R1 = R2 = tBu, E = O (L3)} ligands were synthesized and characterized through elemental analysis, 1H, 13C{1H}, and 27Al NMR spectroscopy, and X-ray crystallography. Reactions of AlMe3 with two equivalents of L1H-L3H gave {[ONER1,R2]2AlMe} (1–3), while reaction of Et2AlCl with two equivalents of L1H and L3H afforded {[ONER1,R2]2AlCl} (4 and 5) as monometallic complexes. The catalytic activity of complexes 1–3 toward ring-opening polymerization (ROP) of ε-caprolactone was assessed. These complexes are more active than analogous Zn complexes for this reaction but less active than the Zn analogues for ROP of rac-lactide. Characteristics of the polymer as well as polymerization kinetics and mechanism were studied. Polymer end-group analyses were achieved using 1H NMR spectroscopy and MALDI-TOF MS. Eyring analyses were performed, and the activation energies for the reactions were determined, which were significantly lower for 1 and 2 compared with 3. This could be for several reasons: (1) the methylamine (NMe) group of 1 and 2, which is a stronger base than the ether (O) group of 3, might activate the incoming monomer via noncovalent interactions, and/or (2) the ether group is able to temporarily coordinate to the metal center and blocks the vacant coordination site toward incoming monomer, while the amine cannot do this. Preliminary studies using 4 and 5 toward copolymerization of cyclohexene oxide with carbon dioxide have been performed. 4 was inactive and 5 afforded polyether carbonate (66.7% epoxide conversion, polymer contains 54.0% carbonate linkages).

Item Type: Article
Item ID: 6057
Department(s): Science, Faculty of > Chemistry
Date: 2012
Date Type: Publication
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