{"id":{"repo_id":"strathclyde","oai_identifier":"oai:strathclyde:jm214p29x"},"canonical_url":"https://search.dev.ndltd.org/etd/strathclyde/oai:strathclyde:jm214p29x","repository":{"repo_id":"strathclyde","name":"University of Strathclyde","base_url":"https://stax.strath.ac.uk/catalog/oai"},"display":{"title":"Advances in alkali-metal-mediated manganation and comparisons with magnesiation","abstract":"The primary aim of this research project was to develop the new concept of Alkali-Metal-Mediated Manganation (AMMMn). Work focused on the reaction of the new Na/Mn alkyl-amido base [(TMEDA)Na(TMP)(CH₂SiMe₃)Mn(TMP)] (16) with a series of organic substrates. Firstly we investigated the reaction of the polymeric dialkyl manganese(II) compound [Mn(CH₂SiMe₃)₂]∞ (1) with a range of Lewis base donors, amines and ketones. The new complexes produced various structural forms ranging from simple monomeric complexes such as [(TMEDA)Mn(CH₂SiMe₃)₂] (2) to more complicated polymeric species such as the dioxane bridged [{(dioxane)[Mn(CH₂SiMe₃)₂]₂}∞] (4). Dialkyl manganese reagent 1 can also function as a deprotonation reagent in its reaction with the primary amine DippNH₂ to afford the trimeric compound [(DippNH)₆Mn₃] (11), while its reaction with benzophenone furnishes the 1,2-addition product [(Me₃SiCH₂)₂Mn₃{μ-OC(CH₂SiMe₃)Ph₂}₄] (13). AMMMn reactions of the synergic base [(TMEDA)Na(TMP)(CH₂SiMe₃)Mn(TMP)] (16) with a variety of functionalised and non-functionalised arene substrates resulted in nine examples of the first reported direct manganations. Highlights include the meta manganation of N, N-dimethylaniline [(TMEDA)Na(TMP)(m-C₆H₄-NMe₂)Mn(TMP)] (21), the para manganation of N, N-diisopropylaniline [(TMEDA)Na(TMP)(p-C₆H₄NiPr₂)Mn(TMP)] (22) and the novel 6-position mangantion of N, N-dimethyl-1-naphthylamine [(TMEDA)Na(TMP){6-(1-Me₂N-C₁₀H₆)}Mn(TMP)] (27). Extending the methodology to Mn(II) based inverse crown complexes proved successful with three new anionic guest molecules, namely a hydride, benzenediide and n-butoxide, successfully being encapsulated within host rings to give three new Mn(II) inverse crown complexes [Na₂Mn₂(μ-H)₂{N(iPr)₂}₄]·(toluene)₂ (31), [(TMEDA)₂Na₂(TMP)₂(1,4-C₆H₄)Mn₂(TMP)₂] (38) and [{(TMEDA)Na(CH₂SiMe₃)(OBu)(o-C₆H₄OMe)Mn}₂] (36) respectively. Remarkably the reaction of the synergic base 16 with the cyclic ether THF results in a new type of cleavage reaction where the C₄ backbone of the THF is cleaved and fourfold deprotonated to furnish a 1, 4-manganated butadiene complex [[(TMEDA)Na(TMP)}₂{1, 4-[Mn(TMP)]₂-C₄H₄}] (42) while the THF O atom is synergically trapped in a separate oxo-inverse crown [Na₂Mn₂(TMP)₄O] (44). The magnetic fingerprints of some of the new Mn(II) compounds are discussed in Chapter 7.","abstract_html":"The primary aim of this research project was to develop the new concept of Alkali-Metal-Mediated Manganation (AMMMn). Work focused on the reaction of the new Na/Mn alkyl-amido base [(TMEDA)Na(TMP)(CH₂SiMe₃)Mn(TMP)] (16) with a series of organic substrates. Firstly we investigated the reaction of the polymeric dialkyl manganese(II) compound [Mn(CH₂SiMe₃)₂]∞ (1) with a range of Lewis base donors, amines and ketones. The new complexes produced various structural forms ranging from simple monomeric complexes such as [(TMEDA)Mn(CH₂SiMe₃)₂] (2) to more complicated polymeric species such as the dioxane bridged [{(dioxane)[Mn(CH₂SiMe₃)₂]₂}∞] (4). Dialkyl manganese reagent 1 can also function as a deprotonation reagent in its reaction with the primary amine DippNH₂ to afford the trimeric compound [(DippNH)₆Mn₃] (11), while its reaction with benzophenone furnishes the 1,2-addition product [(Me₃SiCH₂)₂Mn₃{μ-OC(CH₂SiMe₃)Ph₂}₄] (13). AMMMn reactions of the synergic base [(TMEDA)Na(TMP)(CH₂SiMe₃)Mn(TMP)] (16) with a variety of functionalised and non-functionalised arene substrates resulted in nine examples of the first reported direct manganations. Highlights include the meta manganation of N, N-dimethylaniline [(TMEDA)Na(TMP)(m-C₆H₄-NMe₂)Mn(TMP)] (21), the para manganation of N, N-diisopropylaniline [(TMEDA)Na(TMP)(p-C₆H₄NiPr₂)Mn(TMP)] (22) and the novel 6-position mangantion of N, N-dimethyl-1-naphthylamine [(TMEDA)Na(TMP){6-(1-Me₂N-C₁₀H₆)}Mn(TMP)] (27). Extending the methodology to Mn(II) based inverse crown complexes proved successful with three new anionic guest molecules, namely a hydride, benzenediide and n-butoxide, successfully being encapsulated within host rings to give three new Mn(II) inverse crown complexes [Na₂Mn₂(μ-H)₂{N(iPr)₂}₄]·(toluene)₂ (31), [(TMEDA)₂Na₂(TMP)₂(1,4-C₆H₄)Mn₂(TMP)₂] (38) and [{(TMEDA)Na(CH₂SiMe₃)(OBu)(o-C₆H₄OMe)Mn}₂] (36) respectively. Remarkably the reaction of the synergic base 16 with the cyclic ether THF results in a new type of cleavage reaction where the C₄ backbone of the THF is cleaved and fourfold deprotonated to furnish a 1, 4-manganated butadiene complex [[(TMEDA)Na(TMP)}₂{1, 4-[Mn(TMP)]₂-C₄H₄}] (42) while the THF O atom is synergically trapped in a separate oxo-inverse crown [Na₂Mn₂(TMP)₄O] (44). The magnetic fingerprints of some of the new Mn(II) compounds are discussed in Chapter 7.","abstract_has_math":false,"creators":["Blair, Victoria L."],"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":2010,"date_issued":"2010","date_published":"2010","updated_at":"2026-07-24T04:52:31Z","subjects":[],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier.doi","label":"DOI","values":["10.48730/thrv-rm35"],"render_values":[{"text":"10.48730/thrv-rm35","href":"https://doi.org/10.48730/thrv-rm35","code":true}]},{"key":"dc:identifier","label":"Identifier","values":["T12549"],"render_values":[{"text":"T12549","href":null,"code":true}]}]},"links":{"outbound_url":"https://stax.strath.ac.uk/concern/theses/jm214p29x","outbound_label":"Repository record","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Blair, Victoria L."]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2010"]},{"key":"dc:date.issued","label":"Date","values":["2010"]},{"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":["T12549"]},{"key":"dc:identifier.doi","label":"DOI","values":["10.48730/thrv-rm35"]},{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://stax.strath.ac.uk/concern/theses/jm214p29x"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["The primary aim of this research project was to develop the new concept of Alkali-Metal-Mediated Manganation (AMMMn). Work focused on the reaction of the new Na/Mn alkyl-amido base [(TMEDA)Na(TMP)(CH₂SiMe₃)Mn(TMP)] (16) with a series of organic substrates. Firstly we investigated the reaction of the polymeric dialkyl manganese(II) compound [Mn(CH₂SiMe₃)₂]∞ (1) with a range of Lewis base donors, amines and ketones. The new complexes produced various structural forms ranging from simple monomeric complexes such as [(TMEDA)Mn(CH₂SiMe₃)₂] (2) to more complicated polymeric species such as the dioxane bridged [{(dioxane)[Mn(CH₂SiMe₃)₂]₂}∞] (4). Dialkyl manganese reagent 1 can also function as a deprotonation reagent in its reaction with the primary amine DippNH₂ to afford the trimeric compound [(DippNH)₆Mn₃] (11), while its reaction with benzophenone furnishes the 1,2-addition product [(Me₃SiCH₂)₂Mn₃{μ-OC(CH₂SiMe₃)Ph₂}₄] (13). AMMMn reactions of the synergic base [(TMEDA)Na(TMP)(CH₂SiMe₃)Mn(TMP)] (16) with a variety of functionalised and non-functionalised arene substrates resulted in nine examples of the first reported direct manganations. Highlights include the meta manganation of N, N-dimethylaniline [(TMEDA)Na(TMP)(m-C₆H₄-NMe₂)Mn(TMP)] (21), the para manganation of N, N-diisopropylaniline [(TMEDA)Na(TMP)(p-C₆H₄NiPr₂)Mn(TMP)] (22) and the novel 6-position mangantion of N, N-dimethyl-1-naphthylamine [(TMEDA)Na(TMP){6-(1-Me₂N-C₁₀H₆)}Mn(TMP)] (27). Extending the methodology to Mn(II) based inverse crown complexes proved successful with three new anionic guest molecules, namely a hydride, benzenediide and n-butoxide, successfully being encapsulated within host rings to give three new Mn(II) inverse crown complexes [Na₂Mn₂(μ-H)₂{N(iPr)₂}₄]·(toluene)₂ (31), [(TMEDA)₂Na₂(TMP)₂(1,4-C₆H₄)Mn₂(TMP)₂] (38) and [{(TMEDA)Na(CH₂SiMe₃)(OBu)(o-C₆H₄OMe)Mn}₂] (36) respectively. Remarkably the reaction of the synergic base 16 with the cyclic ether THF results in a new type of cleavage reaction where the C₄ backbone of the THF is cleaved and fourfold deprotonated to furnish a 1, 4-manganated butadiene complex [[(TMEDA)Na(TMP)}₂{1, 4-[Mn(TMP)]₂-C₄H₄}] (42) while the THF O atom is synergically trapped in a separate oxo-inverse crown [Na₂Mn₂(TMP)₄O] (44). The magnetic fingerprints of some of the new Mn(II) compounds are discussed in Chapter 7."]},{"key":"dc:description.abstract","label":"Abstract","values":["The primary aim of this research project was to develop the new concept of Alkali-Metal-Mediated Manganation (AMMMn). Work focused on the reaction of the new Na/Mn alkyl-amido base [(TMEDA)Na(TMP)(CH₂SiMe₃)Mn(TMP)] (16) with a series of organic substrates. Firstly we investigated the reaction of the polymeric dialkyl manganese(II) compound [Mn(CH₂SiMe₃)₂]∞ (1) with a range of Lewis base donors, amines and ketones. The new complexes produced various structural forms ranging from simple monomeric complexes such as [(TMEDA)Mn(CH₂SiMe₃)₂] (2) to more complicated polymeric species such as the dioxane bridged [{(dioxane)[Mn(CH₂SiMe₃)₂]₂}∞] (4). Dialkyl manganese reagent 1 can also function as a deprotonation reagent in its reaction with the primary amine DippNH₂ to afford the trimeric compound [(DippNH)₆Mn₃] (11), while its reaction with benzophenone furnishes the 1,2-addition product [(Me₃SiCH₂)₂Mn₃{μ-OC(CH₂SiMe₃)Ph₂}₄] (13). AMMMn reactions of the synergic base [(TMEDA)Na(TMP)(CH₂SiMe₃)Mn(TMP)] (16) with a variety of functionalised and non-functionalised arene substrates resulted in nine examples of the first reported direct manganations. Highlights include the meta manganation of N, N-dimethylaniline [(TMEDA)Na(TMP)(m-C₆H₄-NMe₂)Mn(TMP)] (21), the para manganation of N, N-diisopropylaniline [(TMEDA)Na(TMP)(p-C₆H₄NiPr₂)Mn(TMP)] (22) and the novel 6-position mangantion of N, N-dimethyl-1-naphthylamine [(TMEDA)Na(TMP){6-(1-Me₂N-C₁₀H₆)}Mn(TMP)] (27). Extending the methodology to Mn(II) based inverse crown complexes proved successful with three new anionic guest molecules, namely a hydride, benzenediide and n-butoxide, successfully being encapsulated within host rings to give three new Mn(II) inverse crown complexes [Na₂Mn₂(μ-H)₂{N(iPr)₂}₄]·(toluene)₂ (31), [(TMEDA)₂Na₂(TMP)₂(1,4-C₆H₄)Mn₂(TMP)₂] (38) and [{(TMEDA)Na(CH₂SiMe₃)(OBu)(o-C₆H₄OMe)Mn}₂] (36) respectively. Remarkably the reaction of the synergic base 16 with the cyclic ether THF results in a new type of cleavage reaction where the C₄ backbone of the THF is cleaved and fourfold deprotonated to furnish a 1, 4-manganated butadiene complex [[(TMEDA)Na(TMP)}₂{1, 4-[Mn(TMP)]₂-C₄H₄}] (42) while the THF O atom is synergically trapped in a separate oxo-inverse crown [Na₂Mn₂(TMP)₄O] (44). The magnetic fingerprints of some of the new Mn(II) compounds are discussed in Chapter 7."]},{"key":"dc:title","label":"Title","values":["Advances in alkali-metal-mediated manganation and comparisons with magnesiation"]}]}],"canonical_facts":{"dc:creator":["Blair, Victoria L."],"dc:date":["2010"],"dc:date.issued":["2010"],"dc:description":["The primary aim of this research project was to develop the new concept of Alkali-Metal-Mediated Manganation (AMMMn). Work focused on the reaction of the new Na/Mn alkyl-amido base [(TMEDA)Na(TMP)(CH₂SiMe₃)Mn(TMP)] (16) with a series of organic substrates. Firstly we investigated the reaction of the polymeric dialkyl manganese(II) compound [Mn(CH₂SiMe₃)₂]∞ (1) with a range of Lewis base donors, amines and ketones. The new complexes produced various structural forms ranging from simple monomeric complexes such as [(TMEDA)Mn(CH₂SiMe₃)₂] (2) to more complicated polymeric species such as the dioxane bridged [{(dioxane)[Mn(CH₂SiMe₃)₂]₂}∞] (4). Dialkyl manganese reagent 1 can also function as a deprotonation reagent in its reaction with the primary amine DippNH₂ to afford the trimeric compound [(DippNH)₆Mn₃] (11), while its reaction with benzophenone furnishes the 1,2-addition product [(Me₃SiCH₂)₂Mn₃{μ-OC(CH₂SiMe₃)Ph₂}₄] (13). AMMMn reactions of the synergic base [(TMEDA)Na(TMP)(CH₂SiMe₃)Mn(TMP)] (16) with a variety of functionalised and non-functionalised arene substrates resulted in nine examples of the first reported direct manganations. Highlights include the meta manganation of N, N-dimethylaniline [(TMEDA)Na(TMP)(m-C₆H₄-NMe₂)Mn(TMP)] (21), the para manganation of N, N-diisopropylaniline [(TMEDA)Na(TMP)(p-C₆H₄NiPr₂)Mn(TMP)] (22) and the novel 6-position mangantion of N, N-dimethyl-1-naphthylamine [(TMEDA)Na(TMP){6-(1-Me₂N-C₁₀H₆)}Mn(TMP)] (27). Extending the methodology to Mn(II) based inverse crown complexes proved successful with three new anionic guest molecules, namely a hydride, benzenediide and n-butoxide, successfully being encapsulated within host rings to give three new Mn(II) inverse crown complexes [Na₂Mn₂(μ-H)₂{N(iPr)₂}₄]·(toluene)₂ (31), [(TMEDA)₂Na₂(TMP)₂(1,4-C₆H₄)Mn₂(TMP)₂] (38) and [{(TMEDA)Na(CH₂SiMe₃)(OBu)(o-C₆H₄OMe)Mn}₂] (36) respectively. Remarkably the reaction of the synergic base 16 with the cyclic ether THF results in a new type of cleavage reaction where the C₄ backbone of the THF is cleaved and fourfold deprotonated to furnish a 1, 4-manganated butadiene complex [[(TMEDA)Na(TMP)}₂{1, 4-[Mn(TMP)]₂-C₄H₄}] (42) while the THF O atom is synergically trapped in a separate oxo-inverse crown [Na₂Mn₂(TMP)₄O] (44). The magnetic fingerprints of some of the new Mn(II) compounds are discussed in Chapter 7."],"dc:description.abstract":["The primary aim of this research project was to develop the new concept of Alkali-Metal-Mediated Manganation (AMMMn). Work focused on the reaction of the new Na/Mn alkyl-amido base [(TMEDA)Na(TMP)(CH₂SiMe₃)Mn(TMP)] (16) with a series of organic substrates. Firstly we investigated the reaction of the polymeric dialkyl manganese(II) compound [Mn(CH₂SiMe₃)₂]∞ (1) with a range of Lewis base donors, amines and ketones. The new complexes produced various structural forms ranging from simple monomeric complexes such as [(TMEDA)Mn(CH₂SiMe₃)₂] (2) to more complicated polymeric species such as the dioxane bridged [{(dioxane)[Mn(CH₂SiMe₃)₂]₂}∞] (4). Dialkyl manganese reagent 1 can also function as a deprotonation reagent in its reaction with the primary amine DippNH₂ to afford the trimeric compound [(DippNH)₆Mn₃] (11), while its reaction with benzophenone furnishes the 1,2-addition product [(Me₃SiCH₂)₂Mn₃{μ-OC(CH₂SiMe₃)Ph₂}₄] (13). AMMMn reactions of the synergic base [(TMEDA)Na(TMP)(CH₂SiMe₃)Mn(TMP)] (16) with a variety of functionalised and non-functionalised arene substrates resulted in nine examples of the first reported direct manganations. Highlights include the meta manganation of N, N-dimethylaniline [(TMEDA)Na(TMP)(m-C₆H₄-NMe₂)Mn(TMP)] (21), the para manganation of N, N-diisopropylaniline [(TMEDA)Na(TMP)(p-C₆H₄NiPr₂)Mn(TMP)] (22) and the novel 6-position mangantion of N, N-dimethyl-1-naphthylamine [(TMEDA)Na(TMP){6-(1-Me₂N-C₁₀H₆)}Mn(TMP)] (27). Extending the methodology to Mn(II) based inverse crown complexes proved successful with three new anionic guest molecules, namely a hydride, benzenediide and n-butoxide, successfully being encapsulated within host rings to give three new Mn(II) inverse crown complexes [Na₂Mn₂(μ-H)₂{N(iPr)₂}₄]·(toluene)₂ (31), [(TMEDA)₂Na₂(TMP)₂(1,4-C₆H₄)Mn₂(TMP)₂] (38) and [{(TMEDA)Na(CH₂SiMe₃)(OBu)(o-C₆H₄OMe)Mn}₂] (36) respectively. Remarkably the reaction of the synergic base 16 with the cyclic ether THF results in a new type of cleavage reaction where the C₄ backbone of the THF is cleaved and fourfold deprotonated to furnish a 1, 4-manganated butadiene complex [[(TMEDA)Na(TMP)}₂{1, 4-[Mn(TMP)]₂-C₄H₄}] (42) while the THF O atom is synergically trapped in a separate oxo-inverse crown [Na₂Mn₂(TMP)₄O] (44). The magnetic fingerprints of some of the new Mn(II) compounds are discussed in Chapter 7."],"dc:identifier":["T12549"],"dc:identifier.doi":["10.48730/thrv-rm35"],"dc:identifier.uri":["https://stax.strath.ac.uk/concern/theses/jm214p29x"],"dc:publisher.department":["Department of Pure and Applied Chemistry"],"dc:publisher.institution":["University of Strathclyde"],"dc:title":["Advances in alkali-metal-mediated manganation and comparisons with magnesiation"],"dc:type.qualificationlevel":["doctoral-pg"],"dc:type.qualificationname":["phd"]},"updated_at":"2026-07-24T04:52:31Z"}