{"id":{"repo_id":"soton","oai_identifier":"oai:eprints.soton.ac.uk:173979"},"canonical_url":"https://search.dev.ndltd.org/etd/soton/oai:eprints.soton.ac.uk:173979","repository":{"repo_id":"soton","name":"University of Southampton","base_url":"https://eprints.soton.ac.uk/cgi/oai2"},"display":{"title":"Carbenoid insertions and cyclometallations of zirconacycles","abstract":"The synthesis of zirconacycles and further elaborations to produce a wide variety of
carbocyclic and heterocyclic systems is well established. This thesis focuses on the
insertion of chloro(aryl)methyllithiums (benzyl carbenoids) into a range of
zirconacyclopentenes and zirconacyclopentanes.
Benzyl carbenoid insertion into a zirconacyclopentene generated the
zirconacyclohexene via a 1,2-metalate rearrangement. A low temperature quench
afforded the expected benzyl inserted product. Quenching at higher temperatures
afforded a styrene containing product. It was proposed that the styrene product was
formed via a novel endocyclic cyclometallation to afford a zirconocene n2-alkene
complex followed by decomplexation. A wide variety of zirconacyclopentenes and
benzyl carbenoids have been investigated.
A range of benzyl carbenoids were inserted into a zirconacyclopentane to afford the
expected benzyl inserted product. Double benzyl carbenoid insertion was also observed
and afforded a mono-alkene product. It was speculated that the bis-inserted products
were formed via a zirconacycloheptane followed by a novel endocyclic
cyclometallation.
Having shown that zirconacyclohexenes underwent an endocyclic cyclometallation to
afford a zirconocene n2-alkene complex, the concept of intramolecular trapping of the
zirconocene n2-alkene complex, to generated bicyclic compounds, was investigated.","abstract_html":"The synthesis of zirconacycles and further elaborations to produce a wide variety of<br/>carbocyclic and heterocyclic systems is well established. This thesis focuses on the<br/>insertion of chloro(aryl)methyllithiums (benzyl carbenoids) into a range of<br/>zirconacyclopentenes and zirconacyclopentanes.<br/><br/>Benzyl carbenoid insertion into a zirconacyclopentene generated the<br/>zirconacyclohexene via a 1,2-metalate rearrangement. A low temperature quench<br/>afforded the expected benzyl inserted product. Quenching at higher temperatures<br/>afforded a styrene containing product. It was proposed that the styrene product was<br/>formed via a novel endocyclic cyclometallation to afford a zirconocene n2-alkene<br/>complex followed by decomplexation. A wide variety of zirconacyclopentenes and<br/>benzyl carbenoids have been investigated.<br/><br/>A range of benzyl carbenoids were inserted into a zirconacyclopentane to afford the<br/>expected benzyl inserted product. Double benzyl carbenoid insertion was also observed<br/>and afforded a mono-alkene product. It was speculated that the bis-inserted products<br/>were formed via a zirconacycloheptane followed by a novel endocyclic<br/>cyclometallation.<br/><br/>Having shown that zirconacyclohexenes underwent an endocyclic cyclometallation to<br/>afford a zirconocene n2-alkene complex, the concept of intramolecular trapping of the<br/>zirconocene n2-alkene complex, to generated bicyclic compounds, was investigated.","abstract_has_math":false,"creators":["Norman, Louise Daisey"],"institution":"University of Southampton","degree_name":"Ph.D.","degree_level":"doctoral","degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":["Whitby, Richard J."],"committee_chairs":[],"committee_members":[],"year":2009,"date_issued":"2009-11","date_published":"2009-11","updated_at":"2026-07-24T04:36:21Z","subjects":[],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":null,"outbound_label":null,"outbound_source":null},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Whitby, Richard J."]},{"key":"dc:creator","label":"Author","values":["Norman, Louise Daisey"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2009-11"]},{"key":"dc:date.issued","label":"Date","values":["2009-11"]},{"key":"dc:publisher.department","label":"Dc Publisher Department","values":["Chemistry (pre 2011 reorg)","School of Chemistry"]},{"key":"dc:publisher.institution","label":"Dc Publisher Institution","values":["University of Southampton"]},{"key":"dc:relation.isreferencedby","label":"Dc Relation Isreferencedby","values":["https://eprints.soton.ac.uk/173979/"]},{"key":"dc:type","label":"Dc Type","values":["Thesis"]},{"key":"dc:type.qualificationlevel","label":"Dc Type Qualificationlevel","values":["doctoral"]},{"key":"dc:type.qualificationname","label":"Dc Type Qualificationname","values":["Ph.D."]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://eprints.soton.ac.uk/173979/1/Louise_Norman_PhD_Thesis.pdf"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["The synthesis of zirconacycles and further elaborations to produce a wide variety of
carbocyclic and heterocyclic systems is well established. This thesis focuses on the
insertion of chloro(aryl)methyllithiums (benzyl carbenoids) into a range of
zirconacyclopentenes and zirconacyclopentanes.
Benzyl carbenoid insertion into a zirconacyclopentene generated the
zirconacyclohexene via a 1,2-metalate rearrangement. A low temperature quench
afforded the expected benzyl inserted product. Quenching at higher temperatures
afforded a styrene containing product. It was proposed that the styrene product was
formed via a novel endocyclic cyclometallation to afford a zirconocene n2-alkene
complex followed by decomplexation. A wide variety of zirconacyclopentenes and
benzyl carbenoids have been investigated.
A range of benzyl carbenoids were inserted into a zirconacyclopentane to afford the
expected benzyl inserted product. Double benzyl carbenoid insertion was also observed
and afforded a mono-alkene product. It was speculated that the bis-inserted products
were formed via a zirconacycloheptane followed by a novel endocyclic
cyclometallation.
Having shown that zirconacyclohexenes underwent an endocyclic cyclometallation to
afford a zirconocene n2-alkene complex, the concept of intramolecular trapping of the
zirconocene n2-alkene complex, to generated bicyclic compounds, was investigated."]},{"key":"dc:format","label":"Dc Format","values":["text"]},{"key":"dc:title","label":"Title","values":["Carbenoid insertions and cyclometallations of zirconacycles"]}]}],"canonical_facts":{"dc:contributor.advisor":["Whitby, Richard J."],"dc:creator":["Norman, Louise Daisey"],"dc:date":["2009-11"],"dc:date.issued":["2009-11"],"dc:description.abstract":["The synthesis of zirconacycles and further elaborations to produce a wide variety of
carbocyclic and heterocyclic systems is well established. This thesis focuses on the
insertion of chloro(aryl)methyllithiums (benzyl carbenoids) into a range of
zirconacyclopentenes and zirconacyclopentanes.
Benzyl carbenoid insertion into a zirconacyclopentene generated the
zirconacyclohexene via a 1,2-metalate rearrangement. A low temperature quench
afforded the expected benzyl inserted product. Quenching at higher temperatures
afforded a styrene containing product. It was proposed that the styrene product was
formed via a novel endocyclic cyclometallation to afford a zirconocene n2-alkene
complex followed by decomplexation. A wide variety of zirconacyclopentenes and
benzyl carbenoids have been investigated.
A range of benzyl carbenoids were inserted into a zirconacyclopentane to afford the
expected benzyl inserted product. Double benzyl carbenoid insertion was also observed
and afforded a mono-alkene product. It was speculated that the bis-inserted products
were formed via a zirconacycloheptane followed by a novel endocyclic
cyclometallation.
Having shown that zirconacyclohexenes underwent an endocyclic cyclometallation to
afford a zirconocene n2-alkene complex, the concept of intramolecular trapping of the
zirconocene n2-alkene complex, to generated bicyclic compounds, was investigated."],"dc:format":["text"],"dc:identifier.uri":["https://eprints.soton.ac.uk/173979/1/Louise_Norman_PhD_Thesis.pdf"],"dc:publisher.department":["Chemistry (pre 2011 reorg)","School of Chemistry"],"dc:publisher.institution":["University of Southampton"],"dc:relation.isreferencedby":["https://eprints.soton.ac.uk/173979/"],"dc:title":["Carbenoid insertions and cyclometallations of zirconacycles"],"dc:type":["Thesis"],"dc:type.qualificationlevel":["doctoral"],"dc:type.qualificationname":["Ph.D."]},"updated_at":"2026-07-24T04:36:21Z"}