{"id":{"repo_id":"lethbridge","oai_identifier":"oai:opus.uleth.ca:10133/7108"},"canonical_url":"https://search.dev.ndltd.org/etd/lethbridge/oai:opus.uleth.ca:10133/7108","repository":{"repo_id":"lethbridge","name":"University of Lethbridge","base_url":"https://opus.uleth.ca/server/oai/request"},"display":{"title":"Donor-stabilised fluorido cations of groups 15 and 16","abstract":"The fluoride-ion donor properties of the strong Lewis-acids SbF5 and AsF5 were investigated. In the presence of the bidentate nitrogen base 1,10-phenanthroline (phen) SbF5 and AsF5 were found to autoionise generating [PnF4(phen)][PnF6] (Pn = As or Sb) salts; this is the first time that SbF5 has demonstrated the ability to act as a fluoride-ion donor. In the presence of the more flexible nitrogen base 2,2′-bipyridine (bipy), SbF5 was again found to autoionise yielding [SbF4(bipy)][SbF6], whereas AsF5 forms the neutral adduct (AsF5)2·bipy. In the presence of the tridentate base 2,2′:6′,2′′-terpyridine (terpy) SbF5 autoionises to form [SbF4(terpy)][SbF6]; the [SbF4(terpy)]+ cation is the first structurally characterised fluorido Sb(V) complex with a coordination number of seven and adopts a heavily distorted pentagonal bipyramidal geometry. The structure and bonding in these unique systems was studied using a combination of spectroscopic, crystallographic and computational techniques. The [SF3]+ cation forms 1:1 adducts with pyridine and 4-dimethylaminopyridine (DMAP) which adopt different structures. Whereas pyridine coordinates in the axial position of the seesaw-geometry, DMAP is located in the equatorial position. The latter structure leads to facile dismutation to the [SF2(dmap)2]2+ cation and SF4, while [SF3(py)]+ is stable towards dismutation. Further dismutation afforded the square-pyramidal [SF(dmap)4]3+ cation. Attempts to form adducts of [SF3]+ cation with triphenylphosphine oxide, resulted in deoxofluorination.","abstract_html":"The fluoride-ion donor properties of the strong Lewis-acids SbF5 and AsF5 were investigated. In the presence of the bidentate nitrogen base 1,10-phenanthroline (phen) SbF5 and AsF5 were found to autoionise generating [PnF4(phen)][PnF6] (Pn = As or Sb) salts; this is the first time that SbF5 has demonstrated the ability to act as a fluoride-ion donor. In the presence of the more flexible nitrogen base 2,2′-bipyridine (bipy), SbF5 was again found to autoionise yielding [SbF4(bipy)][SbF6], whereas AsF5 forms the neutral adduct (AsF5)2·bipy. In the presence of the tridentate base 2,2′:6′,2′′-terpyridine (terpy) SbF5 autoionises to form [SbF4(terpy)][SbF6]; the [SbF4(terpy)]+ cation is the first structurally characterised fluorido Sb(V) complex with a coordination number of seven and adopts a heavily distorted pentagonal bipyramidal geometry. The structure and bonding in these unique systems was studied using a combination of spectroscopic, crystallographic and computational techniques. The [SF3]+ cation forms 1:1 adducts with pyridine and 4-dimethylaminopyridine (DMAP) which adopt different structures. Whereas pyridine coordinates in the axial position of the seesaw-geometry, DMAP is located in the equatorial position. The latter structure leads to facile dismutation to the [SF2(dmap)2]2+ cation and SF4, while [SF3(py)]+ is stable towards dismutation. Further dismutation afforded the square-pyramidal [SF(dmap)4]3+ cation. Attempts to form adducts of [SF3]+ cation with triphenylphosphine oxide, resulted in deoxofluorination.","abstract_has_math":false,"creators":["O'Donnell, Felix","University of Lethbridge. Faculty of Arts and Science"],"institution":"Lethbridge, Alta. : University of Lethbridge, Dept. of Chemistry and Biochemistry","degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":["Gerken, Michael"],"committee_chairs":[],"committee_members":[],"year":2025,"date_issued":"2025","date_published":"2025","updated_at":"2026-08-21T16:45:58Z","subjects":["Fluoride-ion","Lewis-acids","Cation","Main group"],"languages":["en"],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["hdl:10133/7108"],"render_values":[{"text":"hdl:10133/7108","href":null,"code":true}]}]},"links":{"outbound_url":"https://hdl.handle.net/10133/7108","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"source_record":{"url":"https://opus.uleth.ca/server/oai/request?verb=GetRecord&metadataPrefix=dim&identifier=oai%3Aopus.uleth.ca%3A10133%2F7108","prefix":"dim"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.supervisor","label":"Supervisor","values":["Gerken, Michael"]},{"key":"dc:creator","label":"Author","values":["O'Donnell, Felix","University of Lethbridge. 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In the presence of the bidentate nitrogen base 1,10-phenanthroline (phen) SbF5 and AsF5 were found to autoionise generating [PnF4(phen)][PnF6] (Pn = As or Sb) salts; this is the first time that SbF5 has demonstrated the ability to act as a fluoride-ion donor. In the presence of the more flexible nitrogen base 2,2′-bipyridine (bipy), SbF5 was again found to autoionise yielding [SbF4(bipy)][SbF6], whereas AsF5 forms the neutral adduct (AsF5)2·bipy. In the presence of the tridentate base 2,2′:6′,2′′-terpyridine (terpy) SbF5 autoionises to form [SbF4(terpy)][SbF6]; the [SbF4(terpy)]+ cation is the first structurally characterised fluorido Sb(V) complex with a coordination number of seven and adopts a heavily distorted pentagonal bipyramidal geometry. The structure and bonding in these unique systems was studied using a combination of spectroscopic, crystallographic and computational techniques. The [SF3]+ cation forms 1:1 adducts with pyridine and 4-dimethylaminopyridine (DMAP) which adopt different structures. Whereas pyridine coordinates in the axial position of the seesaw-geometry, DMAP is located in the equatorial position. The latter structure leads to facile dismutation to the [SF2(dmap)2]2+ cation and SF4, while [SF3(py)]+ is stable towards dismutation. Further dismutation afforded the square-pyramidal [SF(dmap)4]3+ cation. Attempts to form adducts of [SF3]+ cation with triphenylphosphine oxide, resulted in deoxofluorination."]},{"key":"dc:description.other","label":"Dc Description Other","values":["The fluoride-ion donor properties of the strong Lewis-acids SbF5 and AsF5 were investigated. In the presence of the bidentate nitrogen base 1,10-phenanthroline (phen) SbF5 and AsF5 were found to autoionise generating [PnF4(phen)][PnF6] (Pn = As or Sb) salts; this is the first time that SbF5 has demonstrated the ability to act as a fluoride-ion donor. In the presence of the more flexible nitrogen base 2,2′-bipyridine (bipy), SbF5 was again found to autoionise yielding [SbF4(bipy)][SbF6], whereas AsF5 forms the neutral adduct (AsF5)2·bipy. In the presence of the tridentate base 2,2′:6′,2′′-terpyridine (terpy) SbF5 autoionises to form [SbF4(terpy)][SbF6]; the [SbF4(terpy)]+ cation is the first structurally characterised fluorido Sb(V) complex with a coordination number of seven and adopts a heavily distorted pentagonal bipyramidal geometry. The structure and bonding in these unique systems was studied using a combination of spectroscopic, crystallographic and computational techniques. The [SF3]+ cation forms 1:1 adducts with pyridine and 4-dimethylaminopyridine (DMAP) which adopt different structures. Whereas pyridine coordinates in the axial position of the seesaw-geometry, DMAP is located in the equatorial position. The latter structure leads to facile dismutation to the [SF2(dmap)2]2+ cation and SF4, while [SF3(py)]+ is stable towards dismutation. Further dismutation afforded the square-pyramidal [SF(dmap)4]3+ cation. Attempts to form adducts of [SF3]+ cation with triphenylphosphine oxide, resulted in deoxofluorination."]},{"key":"dc:title","label":"Title","values":["Donor-stabilised fluorido cations of groups 15 and 16"]}]}],"canonical_facts":{"dc:contributor.supervisor":["Gerken, Michael"],"dc:creator":["O'Donnell, Felix","University of Lethbridge. Faculty of Arts and Science"],"dc:date.accessioned":["2025-08-12T20:53:16Z"],"dc:date.available":["2025-08-12T20:53:16Z"],"dc:date.issued":["2025"],"dc:description.abstract":["The fluoride-ion donor properties of the strong Lewis-acids SbF5 and AsF5 were investigated. In the presence of the bidentate nitrogen base 1,10-phenanthroline (phen) SbF5 and AsF5 were found to autoionise generating [PnF4(phen)][PnF6] (Pn = As or Sb) salts; this is the first time that SbF5 has demonstrated the ability to act as a fluoride-ion donor. In the presence of the more flexible nitrogen base 2,2′-bipyridine (bipy), SbF5 was again found to autoionise yielding [SbF4(bipy)][SbF6], whereas AsF5 forms the neutral adduct (AsF5)2·bipy. In the presence of the tridentate base 2,2′:6′,2′′-terpyridine (terpy) SbF5 autoionises to form [SbF4(terpy)][SbF6]; the [SbF4(terpy)]+ cation is the first structurally characterised fluorido Sb(V) complex with a coordination number of seven and adopts a heavily distorted pentagonal bipyramidal geometry. The structure and bonding in these unique systems was studied using a combination of spectroscopic, crystallographic and computational techniques. The [SF3]+ cation forms 1:1 adducts with pyridine and 4-dimethylaminopyridine (DMAP) which adopt different structures. Whereas pyridine coordinates in the axial position of the seesaw-geometry, DMAP is located in the equatorial position. The latter structure leads to facile dismutation to the [SF2(dmap)2]2+ cation and SF4, while [SF3(py)]+ is stable towards dismutation. Further dismutation afforded the square-pyramidal [SF(dmap)4]3+ cation. Attempts to form adducts of [SF3]+ cation with triphenylphosphine oxide, resulted in deoxofluorination."],"dc:description.other":["The fluoride-ion donor properties of the strong Lewis-acids SbF5 and AsF5 were investigated. In the presence of the bidentate nitrogen base 1,10-phenanthroline (phen) SbF5 and AsF5 were found to autoionise generating [PnF4(phen)][PnF6] (Pn = As or Sb) salts; this is the first time that SbF5 has demonstrated the ability to act as a fluoride-ion donor. In the presence of the more flexible nitrogen base 2,2′-bipyridine (bipy), SbF5 was again found to autoionise yielding [SbF4(bipy)][SbF6], whereas AsF5 forms the neutral adduct (AsF5)2·bipy. In the presence of the tridentate base 2,2′:6′,2′′-terpyridine (terpy) SbF5 autoionises to form [SbF4(terpy)][SbF6]; the [SbF4(terpy)]+ cation is the first structurally characterised fluorido Sb(V) complex with a coordination number of seven and adopts a heavily distorted pentagonal bipyramidal geometry. The structure and bonding in these unique systems was studied using a combination of spectroscopic, crystallographic and computational techniques. The [SF3]+ cation forms 1:1 adducts with pyridine and 4-dimethylaminopyridine (DMAP) which adopt different structures. Whereas pyridine coordinates in the axial position of the seesaw-geometry, DMAP is located in the equatorial position. The latter structure leads to facile dismutation to the [SF2(dmap)2]2+ cation and SF4, while [SF3(py)]+ is stable towards dismutation. Further dismutation afforded the square-pyramidal [SF(dmap)4]3+ cation. Attempts to form adducts of [SF3]+ cation with triphenylphosphine oxide, resulted in deoxofluorination."],"dc:identifier":["hdl:10133/7108"],"dc:identifier.uri":["https://hdl.handle.net/10133/7108"],"dc:language.iso":["en"],"dc:publisher":["Lethbridge, Alta. : University of Lethbridge, Dept. of Chemistry and Biochemistry"],"dc:publisher.department":["Department of Chemistry and Biochemistry"],"dc:subject":["Fluoride-ion","Lewis-acids","Cation","Main group"],"dc:title":["Donor-stabilised fluorido cations of groups 15 and 16"],"dc:type":["Thesis"]},"updated_at":"2026-08-21T16:45:58Z"}