title: Novel Ti(IV) and Zr(IV) complexes and their application in the ring-opening polymerisation of cyclic esters.
abstract: A series of group 4 amine tris(phenolate) complexes have been prepared and characterised by single crystal X-ray diffraction and multinuclear NMR spectroscopy. It was found that the ligands afforded monomeric titanium complexes and dimeric zirconium structures in the solid-state. The complexes have been tested for the ring-opening polymerisation of rac-lactide under both solution and melt conditions, which showed varying degrees of selectivity and control, with PDIs in the range of 1.09-2.07. The initiators were also tested for the production of copolymers containing rac-lactide and isosorbide. From NMR spectroscopic analysis and MALDI-TOF mass spectrometry the isosorbide is incorporated into the polymer. The complexes were also screened for the ring-opening polymerisation of 1,3-dioxan-2-one to produce a polycarbonate with good conversions (24-99%).
authors.affiliation: Department of Chemistry, University of Bath, Claverton Down, Bath, UK BA2 7AY.
authors.forename: Emma L
authors.initials: EL
authors.lastname: Whitelaw
authors.forename: Matthew D
authors.initials: MD
authors.lastname: Jones
authors.forename: Mary F
authors.initials: MF
authors.lastname: Mahon
authors.forename: Gabriele
authors.initials: G
authors.lastname: Kociok-Kohn
mesh_terms: D001672:Biocompatible Materials / Q000138:chemical synthesis / Q000737:chemistry; D002254:Carbonates / Q000138:chemical synthesis / Q000737:chemistry; D002412:Cations; D004146:Dioxanes / Q000737:chemistry; D004952:Esters / Q000138:chemical synthesis / Q000737:chemistry*; D006844:Hydrocarbons, Cyclic / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D009942:Organometallic Compounds / Q000737:chemistry*; D011108:Polymers / Q000138:chemical synthesis* / Q000737:chemistry; D019032:Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization; D014025:Titanium / Q000737:chemistry*; D015040:Zirconium / Q000737:chemistry*
chemical_list: D001672:Biocompatible Materials; D002254:Carbonates; D002412:Cations; D004146:Dioxanes; D004952:Esters; D006844:Hydrocarbons, Cyclic; D009942:Organometallic Compounds; D011108:Polymers; D015040:Zirconium; D014025:Titanium