title: Synthesis and characterisation of unsymmetrical Zr(IV) amine tris(phenolate) complexes and their application in ROP of rac-LA.
abstract: Unsymmetrical amine tris(phenolate) ligands have been prepared and complexed to Zr(iv). In the solid-state dimeric species are observed, which persist in solution. The complexes show interesting coordination chemistry and the nature of which is discussed. These complexes are analogues of a highly stereoselective C3-symmetric Zr(iv) amine tris(phenolate) alkoxide and have been prepared, characterised and trialled for the ring-opening of rac-lactide providing insight into the effect of symmetry and ligand steric bulk on selectivity. The polymerisations have been investigated in solution and under the industrially preferred melt conditions (130 °C). The rate law for the ROP has been determined - with Zr2()2(O(i)Pr)2, a pseudo first order dependency was seen, however for Zr2()2(O(i)Pr)2 this changed to a half order dependency in initiator.
authors.affiliation: Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, UK. mj205@bath.ac.uk.
authors.forename: Thomas R
authors.initials: TR
authors.lastname: Forder
authors.forename: Mary F
authors.initials: MF
authors.lastname: Mahon
authors.forename: Matthew G
authors.initials: MG
authors.lastname: Davidson
authors.forename: Timothy
authors.initials: T
authors.lastname: Woodman
authors.forename: Matthew D
authors.initials: MD
authors.lastname: Jones
mesh_terms: D056831:Coordination Complexes / Q000737:chemistry*; D004146:Dioxanes / Q000737:chemistry*; D008024:Ligands; D010636:Phenols / Q000737:chemistry*; D058105:Polymerization; D015040:Zirconium / Q000737:chemistry*
chemical_list: D056831:Coordination Complexes; D004146:Dioxanes; D008024:Ligands; D010636:Phenols; C091880:dilactide; D015040:Zirconium