This thesis describes the synthesis and characterisation of novel mono and dinuclear homogenous [Zn(II)] and [In(III)] metal complexes. Their applications as catalysts for CO<sub>2</sub>/epoxide or epoxide/anhydride ring opening copolymerisation and lactide ring opening polymerisation to generate polycarbonates and polyesters, respectively, are also reported. Chapter 3 reports the first indium phosphasalen catalysts for CO<sub>2</sub>/cyclohexene oxide ring opening copolymerization. The catalysts are active at 1 bar pressure of CO<sub>2</sub> and are most effective without any co-catalyst. It is also possible to use the complexes to isolate and characterise the key intermediates in the catalytic cycle. Kinetic and spectroscopic analyses show that polymerisation proceeds via a rare cis-mononuclear coordination- insertion mechanism. Chapter 4 describes a series of mono and dinuclear zinc macrocycle catalysts with very high activities for the racemic lactide ring opening polymerisation. In most cases, the dinuclear zinc catalysts significantly out-perform the mono-zinc homologue. In addition, kinetic and spectroscopic investigations suggest a role for the ligand conformation in mediating rate. The catalysts perform very well under immortal conditions and operate at low catalyst loading, whilst conserving high activities. Chapter 5 presents four dinuclear zinc acetate salen catalysts for the ring opening copolymerisation of CO<sub>2</sub>/cyclohexene oxide and phthalic anhydride/cyclohexene oxide. The catalysts show moderate activities for CO<sub>2</sub>/epoxide copolymerisation but are highly active for epoxide/anhydride copolymerisation. Structure/activity relationship studies reveal that the more flexible and electron donating ligand displays the highest activity. Poly(ester-b-carbonate)s are also afforded using the most active catalyst in terpolymerisations of anhydride/epoxide/CO<sub>2</sub>.
| Identifer | oai:union.ndltd.org:bl.uk/oai:ethos.bl.uk:740839 |
| Date | January 2017 |
| Creators | Thevenon, Arnaud |
| Contributors | Williams, Charlotte K. |
| Publisher | University of Oxford |
| Source Sets | Ethos UK |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Source | https://ora.ox.ac.uk/objects/uuid:25c312d1-11c9-4180-a62d-b87a41f521c0 |
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