title: Di-Zinc-Aryl Complexes: CO2Insertions and Applications in Polymerisation Catalysis.
abstract: Two new di-zinc-aryl complexes, [LZn2Ph2] and [LZn2(C6F5)2], coordinated by a diphenol tetraamine macrocyclic ligand have been prepared and fully characterised, including by single-crystal X-ray diffraction experiments. The complexes' reactivities with monomers including carbon dioxide, cyclohexene oxide, phthalic anhydride, isopropanol and phenol were investigated using both experimental studies and density functional theory calculations. In particular, [LZn2Ph2] readily inserts carbon dioxide to form a carboxylate, at 1 bar pressure, whereas [LZn2(C6F5)2] does not react. Under these conditions [LZn2Ph2] shows moderate activity in the ring-opening copolymerisation of cyclohexene oxide/carbon dioxide (TOF=20 h-1), cyclohexene oxide/phthalic anhydride (TOF=33 h-1) and the ring-opening polymerisations of rac-lactide (TOF=99 h-1) and ϵ-caprolactone (TOF=5280 h-1).
authors.affiliation: Department of Chemistry, Imperial College London, London, SW7 2AZ, UK.
authors.forename: Charles
authors.identifier: http://orcid.org/0000-0002-1851-8612
authors.initials: C
authors.lastname: Romain
authors.affiliation: EastCHEM School of Chemistry, University of Edinburgh, Edinburgh, EH9 3FJ, UK.
authors.forename: Jennifer A
authors.identifier: http://orcid.org/0000-0002-9027-4931
authors.initials: JA
authors.lastname: Garden
authors.affiliation: Department of Chemistry, Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, Oxford, OX2 3TA, UK.
authors.forename: Gemma
authors.initials: G
authors.lastname: Trott
authors.affiliation: Department of Chemistry, University of Bath, Bath, BA2 7AY, UK.
authors.forename: Antoine
authors.initials: A
authors.lastname: Buchard
authors.affiliation: Department of Chemistry, Imperial College London, London, SW7 2AZ, UK.
authors.forename: Andrew J P
authors.initials: AJP
authors.lastname: White
authors.affiliation: Department of Chemistry, Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, Oxford, OX2 3TA, UK.|Department of Chemistry, Imperial College London, London, SW7 2AZ, UK.
authors.forename: Charlotte K
authors.identifier: http://orcid.org/0000-0002-0734-1575
authors.initials: CK
authors.lastname: Williams
keywords: CO2 insertion; organozinc catalysts; reactivity studies; ring-opening copolymerisation; ring-opening polymerisation; zinc