title: Synthesis of N,N,O-chelate zinc and aluminum complexes and their catalysis in the ring-opening polymerization of ε-caprolactone and rac-lactide.
abstract: Zinc and aluminum complexes supported by N,N,O-chelate ligands were synthesized and characterized. The zinc complexes [Zn(Et){2-{OC(R(1))=CH}-6-(3,5-Me2C3HN2)C5H3N}]2 (R(1) = Ph, 1a; R(1) = Bu(t), 1b) were synthesized by reaction of ligand precursors 2-{R(1)C(O)CH2}-6-(3,5-Me2C3HN2)C5H3N (R(1) = Ph, HL(1); R(1) = Bu(t), HL(2)) with ZnEt2. The aluminum complexes [Al(R)2{2-{OC(Ph)=CH}-6-(3,5-Me2C3HN2)C5H3N}] (R = Me, 2a; R = Et, 2b) were synthesized by reaction of HL(1) with AlMe3 or AlEt3. Similar treatment of the ligand precursor 2-{Ph2C(OH)CH2}-6-(3,5-Me2C3HN2)C5H3N (HL(3)) with AlMe3 or AlEt3 afforded aluminum complexes [Al(R)2{2-{OC(Ph)2CH2}-6-(3,5-Me2C3HN2)C5H3N}] (R = Me, 3a; R = Et, 3b). The complexes were characterized by (1)H and (13)C{(1)H} NMR spectroscopy, elemental analyses and single crystal X-ray diffraction (for 1a, 1b, 2b and 3a). All the complexes are active to catalyze the ring-opening polymerization of ε-caprolactone in the presence of BnOH, leading to polycaprolactone with good molecular weight control and relatively narrow molecular weight distribution. The zinc complexes/BnOH showed good catalytic activity for the ring-opening polymerization of rac-lactide, displaying good molecular weight control and very narrow molecular weight distributions. The PLA catalyzed by complex 1a/BnOH showed somewhat hetero-stereoselectivity with Pr up to 0.73 when the polymerization was performed in THF at 0 °C. Complex 1a/BnOH also catalyzed block copolymerization of ε-CL and rac-LA with good molecular weight control of the polymer. Kinetic studies of the polymerization reactions were performed.
authors.affiliation: CAS Key Laboratory of Soft Matter Chemistry and Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, People's Republic of China. zxwang@ustc.edu.cn.
authors.forename: Wei-Li
authors.initials: WL
authors.lastname: Kong
authors.forename: Zuo-Yun
authors.initials: ZY
authors.lastname: Chai
authors.forename: Zhong-Xia
authors.initials: ZX
authors.lastname: Wang
mesh_terms: D000535:Aluminum / Q000737:chemistry*; D002208:Caproates / Q000737:chemistry*; D002384:Catalysis; D056831:Coordination Complexes / Q000138:chemical synthesis / Q000737:chemistry*; D018360:Crystallography, X-Ray; D004146:Dioxanes / Q000737:chemistry*; D007783:Lactones / Q000737:chemistry*; D008024:Ligands; D008958:Models, Molecular; D058105:Polymerization; D015032:Zinc / Q000737:chemistry*
chemical_list: D002208:Caproates; D056831:Coordination Complexes; D004146:Dioxanes; D007783:Lactones; D008024:Ligands; C121056:caprolactone; C091880:dilactide; D000535:Aluminum; D015032:Zinc