{"id":{"repo_id":"strathclyde","oai_identifier":"oai:strathclyde:2801pg356"},"canonical_url":"https://search.dev.ndltd.org/etd/strathclyde/oai:strathclyde:2801pg356","repository":{"repo_id":"strathclyde","name":"University of Strathclyde","base_url":"https://stax.strath.ac.uk/catalog/oai"},"display":{"title":"Exploiting cooperative effects in s-Block organometallics for new applications in synthesis and catalysis","abstract":"Focussing on group 1 and group 2 metals, this thesis advances the use of polar organometallics in catalysis, in particular intermolecular hydroamination processes; as well as other key stoichiometric transformations, namely deprotonative metallation and C-F bond activation.Group 1 alkyl compounds MCH2SiMe3 (M = Li, Na or K) have proved to be efficient catalysts for intermolecular hydroamination of a wide range of substituted vinylarenes and alkynes at room temperature and with short timescales. Similarly,advancing in the concept of s-block cooperative bimetallic catalysis, alkali-metal magnesiate complexes [MMg(CH2SiMe3)3] and [(donor)2M2Mg(CH2SiMe3)4] (M = Li,Na or K) have shown that they can also act as catalysts for these hydroamination processes, although longer times and high temperature conditions are required in some cases. Reactivity studies show an alkali-metal effect with potassium being significally more reactive than lithium. New insights into the constitution of the potential organometallic intermediates involved in these processes have also been gained by combining X-Ray crystallographic and NMR studies (including DOSY NMR).The second part of this thesis assesses cooperative effects of single-metal organomagnesium complexes in deprotonation and C-F bond activation processes.Using a specially designed metallating base, which combines within the same molecule a sterically demanding β-diketiminate ligand with a kinetically activatedTMP base [DippNacnacMg(TMP)], regioselective magnesiation of heterocyclic and aromatic molecules, including pyrazine or 1,2,4,5-tetrafluorobenzene, can be achieved at room temperature. Structural studies of these metallated intermediates have revealed a crucial stabilising role of the β-diketiminate ligand, which facilitates the trapping of the sensitive anions formed. Additionally, they have provided important clues to rationalise the stability of these species in solution. Contrastingly [DippNacnacMg(THF)Bu] complex is a much more kinetically retarded base, which fails to metallate these substrates promoting in some cases, when confronted with fluoroarenes, C-F bond activation process via nucleophilic aromatic substitution.","abstract_html":"Focussing on group 1 and group 2 metals, this thesis advances the use of polar organometallics in catalysis, in particular intermolecular hydroamination processes; as well as other key stoichiometric transformations, namely deprotonative metallation and C-F bond activation.Group 1 alkyl compounds MCH2SiMe3 (M = Li, Na or K) have proved to be efficient catalysts for intermolecular hydroamination of a wide range of substituted vinylarenes and alkynes at room temperature and with short timescales. Similarly,advancing in the concept of s-block cooperative bimetallic catalysis, alkali-metal magnesiate complexes [MMg(CH2SiMe3)3] and [(donor)2M2Mg(CH2SiMe3)4] (M = Li,Na or K) have shown that they can also act as catalysts for these hydroamination processes, although longer times and high temperature conditions are required in some cases. Reactivity studies show an alkali-metal effect with potassium being significally more reactive than lithium. New insights into the constitution of the potential organometallic intermediates involved in these processes have also been gained by combining X-Ray crystallographic and NMR studies (including DOSY NMR).The second part of this thesis assesses cooperative effects of single-metal organomagnesium complexes in deprotonation and C-F bond activation processes.Using a specially designed metallating base, which combines within the same molecule a sterically demanding β-diketiminate ligand with a kinetically activatedTMP base [DippNacnacMg(TMP)], regioselective magnesiation of heterocyclic and aromatic molecules, including pyrazine or 1,2,4,5-tetrafluorobenzene, can be achieved at room temperature. Structural studies of these metallated intermediates have revealed a crucial stabilising role of the β-diketiminate ligand, which facilitates the trapping of the sensitive anions formed. Additionally, they have provided important clues to rationalise the stability of these species in solution. Contrastingly [DippNacnacMg(THF)Bu] complex is a much more kinetically retarded base, which fails to metallate these substrates promoting in some cases, when confronted with fluoroarenes, C-F bond activation process via nucleophilic aromatic substitution.","abstract_has_math":false,"creators":["Cardona, Laia Davin"],"institution":"University of Strathclyde","degree_name":"phd","degree_level":"doctoral-pg","degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2017,"date_issued":"2017","date_published":"2017","updated_at":"2026-07-24T04:49:47Z","subjects":[],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier.doi","label":"DOI","values":["10.48730/epfd-1916"],"render_values":[{"text":"10.48730/epfd-1916","href":"https://doi.org/10.48730/epfd-1916","code":true}]},{"key":"dc:identifier","label":"Identifier","values":["T14621"],"render_values":[{"text":"T14621","href":null,"code":true}]},{"key":"dc:creator.authoridentifier","label":"Author Identifier","values":["201369876"],"render_values":[{"text":"201369876","href":null,"code":true}]}]},"links":{"outbound_url":"https://stax.strath.ac.uk/concern/theses/2801pg356","outbound_label":"Repository record","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Cardona, Laia Davin"]},{"key":"dc:creator.authoridentifier","label":"Author Identifier","values":["201369876"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2017"]},{"key":"dc:date.issued","label":"Date","values":["2017"]},{"key":"dc:publisher.department","label":"Dc Publisher Department","values":["Department of Pure and Applied Chemistry"]},{"key":"dc:publisher.institution","label":"Dc Publisher Institution","values":["University of Strathclyde"]},{"key":"dc:type.qualificationlevel","label":"Dc Type Qualificationlevel","values":["doctoral-pg"]},{"key":"dc:type.qualificationname","label":"Dc Type Qualificationname","values":["phd"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["T14621"]},{"key":"dc:identifier.doi","label":"DOI","values":["10.48730/epfd-1916"]},{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://stax.strath.ac.uk/concern/theses/2801pg356"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["This thesis was previously restricted to Strathclyde users only from 10 July 2017 until 1 August 2022.","Focussing on group 1 and group 2 metals, this thesis advances the use of polar organometallics in catalysis, in particular intermolecular hydroamination processes; as well as other key stoichiometric transformations, namely deprotonative metallation and C-F bond activation.Group 1 alkyl compounds MCH2SiMe3 (M = Li, Na or K) have proved to be efficient catalysts for intermolecular hydroamination of a wide range of substituted vinylarenes and alkynes at room temperature and with short timescales. Similarly,advancing in the concept of s-block cooperative bimetallic catalysis, alkali-metal magnesiate complexes [MMg(CH2SiMe3)3] and [(donor)2M2Mg(CH2SiMe3)4] (M = Li,Na or K) have shown that they can also act as catalysts for these hydroamination processes, although longer times and high temperature conditions are required in some cases. Reactivity studies show an alkali-metal effect with potassium being significally more reactive than lithium. New insights into the constitution of the potential organometallic intermediates involved in these processes have also been gained by combining X-Ray crystallographic and NMR studies (including DOSY NMR).The second part of this thesis assesses cooperative effects of single-metal organomagnesium complexes in deprotonation and C-F bond activation processes.Using a specially designed metallating base, which combines within the same molecule a sterically demanding β-diketiminate ligand with a kinetically activatedTMP base [DippNacnacMg(TMP)], regioselective magnesiation of heterocyclic and aromatic molecules, including pyrazine or 1,2,4,5-tetrafluorobenzene, can be achieved at room temperature. Structural studies of these metallated intermediates have revealed a crucial stabilising role of the β-diketiminate ligand, which facilitates the trapping of the sensitive anions formed. Additionally, they have provided important clues to rationalise the stability of these species in solution. Contrastingly [DippNacnacMg(THF)Bu] complex is a much more kinetically retarded base, which fails to metallate these substrates promoting in some cases, when confronted with fluoroarenes, C-F bond activation process via nucleophilic aromatic substitution."]},{"key":"dc:description.abstract","label":"Abstract","values":["Focussing on group 1 and group 2 metals, this thesis advances the use of polar organometallics in catalysis, in particular intermolecular hydroamination processes; as well as other key stoichiometric transformations, namely deprotonative metallation and C-F bond activation.Group 1 alkyl compounds MCH2SiMe3 (M = Li, Na or K) have proved to be efficient catalysts for intermolecular hydroamination of a wide range of substituted vinylarenes and alkynes at room temperature and with short timescales. Similarly,advancing in the concept of s-block cooperative bimetallic catalysis, alkali-metal magnesiate complexes [MMg(CH2SiMe3)3] and [(donor)2M2Mg(CH2SiMe3)4] (M = Li,Na or K) have shown that they can also act as catalysts for these hydroamination processes, although longer times and high temperature conditions are required in some cases. Reactivity studies show an alkali-metal effect with potassium being significally more reactive than lithium. New insights into the constitution of the potential organometallic intermediates involved in these processes have also been gained by combining X-Ray crystallographic and NMR studies (including DOSY NMR).The second part of this thesis assesses cooperative effects of single-metal organomagnesium complexes in deprotonation and C-F bond activation processes.Using a specially designed metallating base, which combines within the same molecule a sterically demanding β-diketiminate ligand with a kinetically activatedTMP base [DippNacnacMg(TMP)], regioselective magnesiation of heterocyclic and aromatic molecules, including pyrazine or 1,2,4,5-tetrafluorobenzene, can be achieved at room temperature. Structural studies of these metallated intermediates have revealed a crucial stabilising role of the β-diketiminate ligand, which facilitates the trapping of the sensitive anions formed. Additionally, they have provided important clues to rationalise the stability of these species in solution. Contrastingly [DippNacnacMg(THF)Bu] complex is a much more kinetically retarded base, which fails to metallate these substrates promoting in some cases, when confronted with fluoroarenes, C-F bond activation process via nucleophilic aromatic substitution."]},{"key":"dc:title","label":"Title","values":["Exploiting cooperative effects in s-Block organometallics for new applications in synthesis and catalysis"]}]}],"canonical_facts":{"dc:creator":["Cardona, Laia Davin"],"dc:creator.authoridentifier":["201369876"],"dc:date":["2017"],"dc:date.issued":["2017"],"dc:description":["This thesis was previously restricted to Strathclyde users only from 10 July 2017 until 1 August 2022.","Focussing on group 1 and group 2 metals, this thesis advances the use of polar organometallics in catalysis, in particular intermolecular hydroamination processes; as well as other key stoichiometric transformations, namely deprotonative metallation and C-F bond activation.Group 1 alkyl compounds MCH2SiMe3 (M = Li, Na or K) have proved to be efficient catalysts for intermolecular hydroamination of a wide range of substituted vinylarenes and alkynes at room temperature and with short timescales. Similarly,advancing in the concept of s-block cooperative bimetallic catalysis, alkali-metal magnesiate complexes [MMg(CH2SiMe3)3] and [(donor)2M2Mg(CH2SiMe3)4] (M = Li,Na or K) have shown that they can also act as catalysts for these hydroamination processes, although longer times and high temperature conditions are required in some cases. Reactivity studies show an alkali-metal effect with potassium being significally more reactive than lithium. New insights into the constitution of the potential organometallic intermediates involved in these processes have also been gained by combining X-Ray crystallographic and NMR studies (including DOSY NMR).The second part of this thesis assesses cooperative effects of single-metal organomagnesium complexes in deprotonation and C-F bond activation processes.Using a specially designed metallating base, which combines within the same molecule a sterically demanding β-diketiminate ligand with a kinetically activatedTMP base [DippNacnacMg(TMP)], regioselective magnesiation of heterocyclic and aromatic molecules, including pyrazine or 1,2,4,5-tetrafluorobenzene, can be achieved at room temperature. Structural studies of these metallated intermediates have revealed a crucial stabilising role of the β-diketiminate ligand, which facilitates the trapping of the sensitive anions formed. Additionally, they have provided important clues to rationalise the stability of these species in solution. Contrastingly [DippNacnacMg(THF)Bu] complex is a much more kinetically retarded base, which fails to metallate these substrates promoting in some cases, when confronted with fluoroarenes, C-F bond activation process via nucleophilic aromatic substitution."],"dc:description.abstract":["Focussing on group 1 and group 2 metals, this thesis advances the use of polar organometallics in catalysis, in particular intermolecular hydroamination processes; as well as other key stoichiometric transformations, namely deprotonative metallation and C-F bond activation.Group 1 alkyl compounds MCH2SiMe3 (M = Li, Na or K) have proved to be efficient catalysts for intermolecular hydroamination of a wide range of substituted vinylarenes and alkynes at room temperature and with short timescales. Similarly,advancing in the concept of s-block cooperative bimetallic catalysis, alkali-metal magnesiate complexes [MMg(CH2SiMe3)3] and [(donor)2M2Mg(CH2SiMe3)4] (M = Li,Na or K) have shown that they can also act as catalysts for these hydroamination processes, although longer times and high temperature conditions are required in some cases. Reactivity studies show an alkali-metal effect with potassium being significally more reactive than lithium. New insights into the constitution of the potential organometallic intermediates involved in these processes have also been gained by combining X-Ray crystallographic and NMR studies (including DOSY NMR).The second part of this thesis assesses cooperative effects of single-metal organomagnesium complexes in deprotonation and C-F bond activation processes.Using a specially designed metallating base, which combines within the same molecule a sterically demanding β-diketiminate ligand with a kinetically activatedTMP base [DippNacnacMg(TMP)], regioselective magnesiation of heterocyclic and aromatic molecules, including pyrazine or 1,2,4,5-tetrafluorobenzene, can be achieved at room temperature. Structural studies of these metallated intermediates have revealed a crucial stabilising role of the β-diketiminate ligand, which facilitates the trapping of the sensitive anions formed. Additionally, they have provided important clues to rationalise the stability of these species in solution. Contrastingly [DippNacnacMg(THF)Bu] complex is a much more kinetically retarded base, which fails to metallate these substrates promoting in some cases, when confronted with fluoroarenes, C-F bond activation process via nucleophilic aromatic substitution."],"dc:identifier":["T14621"],"dc:identifier.doi":["10.48730/epfd-1916"],"dc:identifier.uri":["https://stax.strath.ac.uk/concern/theses/2801pg356"],"dc:publisher.department":["Department of Pure and Applied Chemistry"],"dc:publisher.institution":["University of Strathclyde"],"dc:title":["Exploiting cooperative effects in s-Block organometallics for new applications in synthesis and catalysis"],"dc:type.qualificationlevel":["doctoral-pg"],"dc:type.qualificationname":["phd"]},"updated_at":"2026-07-24T04:49:47Z"}