Group 4 amidinate complexes as olefin polymerisation catalysts
<p>This Thesis describes the syntheses, structure and olefin polymerisation capability of a series of group 4 ?1-amidinate-supported complexes. Chapter One introduces metal-catalysed polymerisation of olefins with emphasis on the development of homogeneous molecular catalysts. The evolution of...
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| Format: | Thesis |
| Language: | English |
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2016
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| _version_ | 1826277080570003456 |
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| author | Scott, R |
| author2 | Mountford, P |
| author_facet | Mountford, P Scott, R |
| author_sort | Scott, R |
| collection | OXFORD |
| description | <p>This Thesis describes the syntheses, structure and olefin polymerisation capability of a series of group 4 ?1-amidinate-supported complexes. Chapter One introduces metal-catalysed polymerisation of olefins with emphasis on the development of homogeneous molecular catalysts. The evolution of ?post-metallocene? systems, cocatalysts and the chemistry of activation are explored providing context to the work detailed in subsequent chapters.</p> <p>Chapter Two describes the synthesis and characterisation of new titanium cyclopentadienyl-amidinate diene complexes and corresponding B(C6F5)3-activated zwitterionic compounds. Their performance in small-scale ethylene-propylene-diene monomer (EPDM) copolymerisation is compared to that of a related dialkyl initiator. Some underlying chemistry of the diene/zwitterionic species is explored particularly in relation to the reversibility of zwitterion formation (activation).</p> <p>Chapter Three details the synthesis and characterisation of a congeneric series of cyclopentadienyl-amidinate group 4 complexes. Combined crystallographic and DFT studies provide an insight into the nature of the amidinate-metal interaction as well as the bonding and conformational preference of the diene complexes described in Chapters Two and Three. The performance of these precatalysts in ethylene homo- and ethylene-propylene (EP) copolymerisation experiments is presented along with preliminary activation experiments giving enhanced understanding of the nature of the active species.</p> <p>Chapter Four describes the synthesis and characterisation of a series of chelating cyclopentadienyl-amidinate complexes. Structural characterisation of these compounds combined with DFT calculations provide useful comparisons with the related non-ansa precatalysts. The EP and EPDM polymerisation performance of the bridged complexes is compared to a representative non-chelated precatalyst.</p> <p>Chapter Five contains experimental details and characterising data for new compounds described in this Thesis.</p> <p>CD Appendix provides crystallography .cif files.</p> |
| first_indexed | 2024-03-06T23:23:31Z |
| format | Thesis |
| id | oxford-uuid:69980bfb-d3bf-4232-9580-c661bf92c1ec |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-06T23:23:31Z |
| publishDate | 2016 |
| record_format | dspace |
| spelling | oxford-uuid:69980bfb-d3bf-4232-9580-c661bf92c1ec2022-03-26T18:51:54ZGroup 4 amidinate complexes as olefin polymerisation catalystsThesishttp://purl.org/coar/resource_type/c_db06uuid:69980bfb-d3bf-4232-9580-c661bf92c1ecOrganometallic ChemistryEnglishOxford University Research Archive - Valet2016Scott, RMountford, P<p>This Thesis describes the syntheses, structure and olefin polymerisation capability of a series of group 4 ?1-amidinate-supported complexes. Chapter One introduces metal-catalysed polymerisation of olefins with emphasis on the development of homogeneous molecular catalysts. The evolution of ?post-metallocene? systems, cocatalysts and the chemistry of activation are explored providing context to the work detailed in subsequent chapters.</p> <p>Chapter Two describes the synthesis and characterisation of new titanium cyclopentadienyl-amidinate diene complexes and corresponding B(C6F5)3-activated zwitterionic compounds. Their performance in small-scale ethylene-propylene-diene monomer (EPDM) copolymerisation is compared to that of a related dialkyl initiator. Some underlying chemistry of the diene/zwitterionic species is explored particularly in relation to the reversibility of zwitterion formation (activation).</p> <p>Chapter Three details the synthesis and characterisation of a congeneric series of cyclopentadienyl-amidinate group 4 complexes. Combined crystallographic and DFT studies provide an insight into the nature of the amidinate-metal interaction as well as the bonding and conformational preference of the diene complexes described in Chapters Two and Three. The performance of these precatalysts in ethylene homo- and ethylene-propylene (EP) copolymerisation experiments is presented along with preliminary activation experiments giving enhanced understanding of the nature of the active species.</p> <p>Chapter Four describes the synthesis and characterisation of a series of chelating cyclopentadienyl-amidinate complexes. Structural characterisation of these compounds combined with DFT calculations provide useful comparisons with the related non-ansa precatalysts. The EP and EPDM polymerisation performance of the bridged complexes is compared to a representative non-chelated precatalyst.</p> <p>Chapter Five contains experimental details and characterising data for new compounds described in this Thesis.</p> <p>CD Appendix provides crystallography .cif files.</p> |
| spellingShingle | Organometallic Chemistry Scott, R Group 4 amidinate complexes as olefin polymerisation catalysts |
| title | Group 4 amidinate complexes as olefin polymerisation catalysts |
| title_full | Group 4 amidinate complexes as olefin polymerisation catalysts |
| title_fullStr | Group 4 amidinate complexes as olefin polymerisation catalysts |
| title_full_unstemmed | Group 4 amidinate complexes as olefin polymerisation catalysts |
| title_short | Group 4 amidinate complexes as olefin polymerisation catalysts |
| title_sort | group 4 amidinate complexes as olefin polymerisation catalysts |
| topic | Organometallic Chemistry |
| work_keys_str_mv | AT scottr group4amidinatecomplexesasolefinpolymerisationcatalysts |