{"id":{"repo_id":"uwo","oai_identifier":"oai:uwo.scholaris.ca:20.500.14721/19495"},"canonical_url":"https://search.dev.ndltd.org/etd/uwo/oai:uwo.scholaris.ca:20.500.14721/19495","repository":{"repo_id":"uwo","name":"Western University","base_url":"https://uwo.scholaris.ca/server/oai/request"},"display":{"title":"INTERMOLECULAR COMPLEXES OF GERMANIUM(II","abstract":"This thesis examines the synthesis, structural characterization, and reactivity of neutral and charged intermolecular donor complexes of germanium(II). Base stabilized complexes of dimesitylgermylene (Mes2Ge) (mes = mesityl = 2,4,6- trimethylphenyl) with either an anionic diisopropylphenyl-substituted N-heterocyclic gallium® (NHGa') ligand or a diisopropyl substituted N-heterocyclic carbene (NHC) ligand were synthesized by the addition of two equivalents of either NHGa' or NHC to tetramesityldigermene (Mes2Ge=GeMes2). The complexes [NHGa-GeMes2] and NHC- GeMes2 are the first two examples of a transient germylene (Mes2Ge) being stabilized by intermolecular donors. A series of NHC complexes of GefG (R = F, Cl, Br, I, CI/O3SCF3,0'Bu, NCS, Mes) were synthesized. The !H NMR spectra of the NHC-GeR2 complexes show broad signals at room temperature which was rationalized by either conformational interchanges or intermolecular exchanges. The NHC-GeR2 complexes were also examinedcomputationally. Theenergyofcomplexationwasfoundtodecreaseif7T donor atoms are located adjacent to the germanium centre. The reactivity of selected NHC-GeR2 (R = Cl, OlBu, or Mes) complexes towards 2,3-dimethylbutadiene, S^-di-Wtyl-orthoquinone, methyl iodide, pivalic acid and benzophenone was examined. In comparison with uncomplexed GeR2 species, the NHC-GeR2 complexes are less reactive. The prospect of using the NHC-GeR2 complexes as a synthon for GeR2 appears to be reaction specific. Finally, a series of cationic germanium(II) complexes were synthesized and characterized, including examples of germanium(II) centred dications. A germanium 111 centred dication supported by three NHC ligands [NHC3Ge][I]2 was characterized and examined computationally. The structure of (cryptand[2.2.2]Ge) , as the inflate salt, was reported and is the first example of a non-metal cation situated within a cryptand. A number cationic germanium crown ether complexes were are also synthesized including [[12]crown-4)2*Ge]2+, [[15]crown-5*GeOTf]+ and [benzo[15]crown-5•GeC1]+ and [benzo[15]crown-5•GeOTf. The geometries of the crown ether-germanium complexes were found to be highly dependent on the size of the crown ether and the substituent located on the germanium.","abstract_html":"This thesis examines the synthesis, structural characterization, and reactivity of neutral and charged intermolecular donor complexes of germanium(II). Base stabilized complexes of dimesitylgermylene (Mes2Ge) (mes = mesityl = 2,4,6- trimethylphenyl) with either an anionic diisopropylphenyl-substituted N-heterocyclic gallium® (NHGa') ligand or a diisopropyl substituted N-heterocyclic carbene (NHC) ligand were synthesized by the addition of two equivalents of either NHGa' or NHC to tetramesityldigermene (Mes2Ge=GeMes2). The complexes [NHGa-GeMes2] and NHC- GeMes2 are the first two examples of a transient germylene (Mes2Ge) being stabilized by intermolecular donors. A series of NHC complexes of GefG (R = F, Cl, Br, I, CI/O3SCF3,0'Bu, NCS, Mes) were synthesized. The !H NMR spectra of the NHC-GeR2 complexes show broad signals at room temperature which was rationalized by either conformational interchanges or intermolecular exchanges. The NHC-GeR2 complexes were also examinedcomputationally. Theenergyofcomplexationwasfoundtodecreaseif7T donor atoms are located adjacent to the germanium centre. The reactivity of selected NHC-GeR2 (R = Cl, OlBu, or Mes) complexes towards 2,3-dimethylbutadiene, S^-di-Wtyl-orthoquinone, methyl iodide, pivalic acid and benzophenone was examined. In comparison with uncomplexed GeR2 species, the NHC-GeR2 complexes are less reactive. The prospect of using the NHC-GeR2 complexes as a synthon for GeR2 appears to be reaction specific. Finally, a series of cationic germanium(II) complexes were synthesized and characterized, including examples of germanium(II) centred dications. A germanium 111 centred dication supported by three NHC ligands [NHC3Ge][I]2 was characterized and examined computationally. The structure of (cryptand[2.2.2]Ge) , as the inflate salt, was reported and is the first example of a non-metal cation situated within a cryptand. A number cationic germanium crown ether complexes were are also synthesized including [[12]crown-4)2*Ge]2+, [[15]crown-5*GeOTf]+ and [benzo[15]crown-5•GeC1]+ and [benzo[15]crown-5•GeOTf. The geometries of the crown ether-germanium complexes were found to be highly dependent on the size of the crown ether and the substituent located on the germanium.","abstract_has_math":false,"creators":["Rupar, Paul A."],"institution":null,"degree_name":"Ph D","degree_level":null,"degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":[],"advisors":["Baines, Kim"],"committee_chairs":[],"committee_members":[],"year":2009,"date_issued":"2009-01-01","date_published":"2009-01-01","updated_at":"2026-07-27T21:56:09Z","subjects":["germylene","germanium(II)","N-heterocyclic carbene","base stabilized","crystal structure","crown ether","cryptand","gallium(I"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://hdl.handle.net/20.500.14721/19495","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Baines, Kim"]},{"key":"dc:creator","label":"Author","values":["Rupar, Paul A."]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2025-06-25T19:04:02Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2025-06-25T19:04:02Z"]},{"key":"dc:date.issued","label":"Date","values":["2009-01-01"]},{"key":"dc:type","label":"Dc Type","values":["thesis"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Ph D"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["germylene","germanium(II)","N-heterocyclic carbene","base stabilized","crystal structure","crown ether","cryptand","gallium(I"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://hdl.handle.net/20.500.14721/19495"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["This thesis examines the synthesis, structural characterization, and reactivity of neutral and charged intermolecular donor complexes of germanium(II). Base stabilized complexes of dimesitylgermylene (Mes2Ge) (mes = mesityl = 2,4,6- trimethylphenyl) with either an anionic diisopropylphenyl-substituted N-heterocyclic gallium® (NHGa') ligand or a diisopropyl substituted N-heterocyclic carbene (NHC) ligand were synthesized by the addition of two equivalents of either NHGa' or NHC to tetramesityldigermene (Mes2Ge=GeMes2). The complexes [NHGa-GeMes2] and NHC- GeMes2 are the first two examples of a transient germylene (Mes2Ge) being stabilized by intermolecular donors. A series of NHC complexes of GefG (R = F, Cl, Br, I, CI/O3SCF3,0'Bu, NCS, Mes) were synthesized. The !H NMR spectra of the NHC-GeR2 complexes show broad signals at room temperature which was rationalized by either conformational interchanges or intermolecular exchanges. The NHC-GeR2 complexes were also examinedcomputationally. Theenergyofcomplexationwasfoundtodecreaseif7T donor atoms are located adjacent to the germanium centre. The reactivity of selected NHC-GeR2 (R = Cl, OlBu, or Mes) complexes towards 2,3-dimethylbutadiene, S^-di-Wtyl-orthoquinone, methyl iodide, pivalic acid and benzophenone was examined. In comparison with uncomplexed GeR2 species, the NHC-GeR2 complexes are less reactive. The prospect of using the NHC-GeR2 complexes as a synthon for GeR2 appears to be reaction specific. Finally, a series of cationic germanium(II) complexes were synthesized and characterized, including examples of germanium(II) centred dications. A germanium 111 centred dication supported by three NHC ligands [NHC3Ge][I]2 was characterized and examined computationally. The structure of (cryptand[2.2.2]Ge) , as the inflate salt, was reported and is the first example of a non-metal cation situated within a cryptand. A number cationic germanium crown ether complexes were are also synthesized including [[12]crown-4)2*Ge]2+, [[15]crown-5*GeOTf]+ and [benzo[15]crown-5•GeC1]+ and [benzo[15]crown-5•GeOTf. The geometries of the crown ether-germanium complexes were found to be highly dependent on the size of the crown ether and the substituent located on the germanium."]},{"key":"dc:title","label":"Title","values":["INTERMOLECULAR COMPLEXES OF GERMANIUM(II"]}]}],"canonical_facts":{"dc:contributor.advisor":["Baines, Kim"],"dc:creator":["Rupar, Paul A."],"dc:date.accessioned":["2025-06-25T19:04:02Z"],"dc:date.available":["2025-06-25T19:04:02Z"],"dc:date.issued":["2009-01-01"],"dc:description.abstract":["This thesis examines the synthesis, structural characterization, and reactivity of neutral and charged intermolecular donor complexes of germanium(II). Base stabilized complexes of dimesitylgermylene (Mes2Ge) (mes = mesityl = 2,4,6- trimethylphenyl) with either an anionic diisopropylphenyl-substituted N-heterocyclic gallium® (NHGa') ligand or a diisopropyl substituted N-heterocyclic carbene (NHC) ligand were synthesized by the addition of two equivalents of either NHGa' or NHC to tetramesityldigermene (Mes2Ge=GeMes2). The complexes [NHGa-GeMes2] and NHC- GeMes2 are the first two examples of a transient germylene (Mes2Ge) being stabilized by intermolecular donors. A series of NHC complexes of GefG (R = F, Cl, Br, I, CI/O3SCF3,0'Bu, NCS, Mes) were synthesized. The !H NMR spectra of the NHC-GeR2 complexes show broad signals at room temperature which was rationalized by either conformational interchanges or intermolecular exchanges. The NHC-GeR2 complexes were also examinedcomputationally. Theenergyofcomplexationwasfoundtodecreaseif7T donor atoms are located adjacent to the germanium centre. The reactivity of selected NHC-GeR2 (R = Cl, OlBu, or Mes) complexes towards 2,3-dimethylbutadiene, S^-di-Wtyl-orthoquinone, methyl iodide, pivalic acid and benzophenone was examined. In comparison with uncomplexed GeR2 species, the NHC-GeR2 complexes are less reactive. The prospect of using the NHC-GeR2 complexes as a synthon for GeR2 appears to be reaction specific. Finally, a series of cationic germanium(II) complexes were synthesized and characterized, including examples of germanium(II) centred dications. A germanium 111 centred dication supported by three NHC ligands [NHC3Ge][I]2 was characterized and examined computationally. The structure of (cryptand[2.2.2]Ge) , as the inflate salt, was reported and is the first example of a non-metal cation situated within a cryptand. A number cationic germanium crown ether complexes were are also synthesized including [[12]crown-4)2*Ge]2+, [[15]crown-5*GeOTf]+ and [benzo[15]crown-5•GeC1]+ and [benzo[15]crown-5•GeOTf. The geometries of the crown ether-germanium complexes were found to be highly dependent on the size of the crown ether and the substituent located on the germanium."],"dc:identifier.uri":["https://hdl.handle.net/20.500.14721/19495"],"dc:subject":["germylene","germanium(II)","N-heterocyclic carbene","base stabilized","crystal structure","crown ether","cryptand","gallium(I"],"dc:title":["INTERMOLECULAR COMPLEXES OF GERMANIUM(II"],"dc:type":["thesis"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_name":["Ph D"]},"updated_at":"2026-07-27T21:56:09Z"}