{"id":{"repo_id":"lethbridge","oai_identifier":"oai:opus.uleth.ca:10133/5195"},"canonical_url":"https://search.dev.ndltd.org/etd/lethbridge/oai:opus.uleth.ca:10133/5195","repository":{"repo_id":"lethbridge","name":"University of Lethbridge","base_url":"https://opus.uleth.ca/server/oai/request"},"display":{"title":"A study of proposed intermediates in the deoxofluorination of carbonyl groups by SF4","abstract":"The [SF4·O=C(CH3)2]2 and SF4·[O=C(CH3)2]2 adducts were synthesized and characterized at low temperature (LT) using Raman spectroscopy and, in the case of [SF4·O=C(CH3)2]2, single-crystal X-ray diffraction. The X-ray crystal structure of SF4·(O=C10H14)·(HF) was obtained, showing F4S---F−H---O=C10H14 interactions. Adducts of [SF3]+ with acetone, cyclopentanone, and 2-adamantanone were shown by 19F and 1H NMR spectroscopy to exist in solutions below −40 °C. The proposed [SF3·{O=C(CH3)2}3]+ cation was observed at LT by reacting [SF3][AsF6] with excess acetone. Above −40 °C SF4 formation was observed. Protonated ketones, [HO=R]+ (R = C(CH3)2, C5H8, C10H14), and aldehydes, [H(O=CHC6H5)2]+ and [H(O=CHCH3)x]+ (x = 1 or 2), were isolated and characterized in the solid state for the first time. NBO analyses were used to quantify the increase in electrophilicity of the oxonium cations. The AsF5·O=R (R = C(CH3)2, C5H8, C10H14) adducts were synthesized and characterized in solution and solid state using LT NMR and Raman spectroscopies, respectively.","abstract_html":"The [SF4·O=C(CH3)2]2 and SF4·[O=C(CH3)2]2 adducts were synthesized and characterized at low temperature (LT) using Raman spectroscopy and, in the case of [SF4·O=C(CH3)2]2, single-crystal X-ray diffraction. The X-ray crystal structure of SF4·(O=C10H14)·(HF) was obtained, showing F4S---F−H---O=C10H14 interactions. Adducts of [SF3]+ with acetone, cyclopentanone, and 2-adamantanone were shown by 19F and 1H NMR spectroscopy to exist in solutions below −40 °C. The proposed [SF3·{O=C(CH3)2}3]+ cation was observed at LT by reacting [SF3][AsF6] with excess acetone. Above −40 °C SF4 formation was observed. Protonated ketones, [HO=R]+ (R = C(CH3)2, C5H8, C10H14), and aldehydes, [H(O=CHC6H5)2]+ and [H(O=CHCH3)x]+ (x = 1 or 2), were isolated and characterized in the solid state for the first time. NBO analyses were used to quantify the increase in electrophilicity of the oxonium cations. The AsF5·O=R (R = C(CH3)2, C5H8, C10H14) adducts were synthesized and characterized in solution and solid state using LT NMR and Raman spectroscopies, respectively.","abstract_has_math":false,"creators":["Stuart, Daniel","University of Lethbridge. Faculty of Arts and Science"],"institution":null,"degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2018,"date_issued":"2018","date_published":"2018","updated_at":"2026-07-27T20:02:41Z","subjects":["Organofluorine compounds","Sulfur tetrafluoride","Carbonyl compounds","Lewis acids","deoxofluorination reactions","Lewis acid-base reactions","organic carbonyl compounds","organofluorine chemistry"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["hdl:10133/5195"],"render_values":[{"text":"hdl:10133/5195","href":null,"code":true}]}]},"links":{"outbound_url":null,"outbound_label":null,"outbound_source":null},"metadata_groups":[{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.issued","label":"Date","values":["2018"]},{"key":"dc:type","label":"Dc Type","values":["Thesis"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Organofluorine compounds","Sulfur tetrafluoride","Carbonyl compounds","Lewis acids","deoxofluorination reactions","Lewis acid-base reactions","organic carbonyl compounds","organofluorine chemistry"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["hdl:10133/5195"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.other","label":"Dc Description Other","values":["The [SF4·O=C(CH3)2]2 and SF4·[O=C(CH3)2]2 adducts were synthesized and characterized at low temperature (LT) using Raman spectroscopy and, in the case of [SF4·O=C(CH3)2]2, single-crystal X-ray diffraction. The X-ray crystal structure of SF4·(O=C10H14)·(HF) was obtained, showing F4S---F−H---O=C10H14 interactions. Adducts of [SF3]+ with acetone, cyclopentanone, and 2-adamantanone were shown by 19F and 1H NMR spectroscopy to exist in solutions below −40 °C. The proposed [SF3·{O=C(CH3)2}3]+ cation was observed at LT by reacting [SF3][AsF6] with excess acetone. Above −40 °C SF4 formation was observed. Protonated ketones, [HO=R]+ (R = C(CH3)2, C5H8, C10H14), and aldehydes, [H(O=CHC6H5)2]+ and [H(O=CHCH3)x]+ (x = 1 or 2), were isolated and characterized in the solid state for the first time. NBO analyses were used to quantify the increase in electrophilicity of the oxonium cations. The AsF5·O=R (R = C(CH3)2, C5H8, C10H14) adducts were synthesized and characterized in solution and solid state using LT NMR and Raman spectroscopies, respectively."]},{"key":"dc:title","label":"Title","values":["A study of proposed intermediates in the deoxofluorination of carbonyl groups by SF4"]}]}],"canonical_facts":{"dc:date.issued":["2018"],"dc:description.other":["The [SF4·O=C(CH3)2]2 and SF4·[O=C(CH3)2]2 adducts were synthesized and characterized at low temperature (LT) using Raman spectroscopy and, in the case of [SF4·O=C(CH3)2]2, single-crystal X-ray diffraction. The X-ray crystal structure of SF4·(O=C10H14)·(HF) was obtained, showing F4S---F−H---O=C10H14 interactions. Adducts of [SF3]+ with acetone, cyclopentanone, and 2-adamantanone were shown by 19F and 1H NMR spectroscopy to exist in solutions below −40 °C. The proposed [SF3·{O=C(CH3)2}3]+ cation was observed at LT by reacting [SF3][AsF6] with excess acetone. Above −40 °C SF4 formation was observed. Protonated ketones, [HO=R]+ (R = C(CH3)2, C5H8, C10H14), and aldehydes, [H(O=CHC6H5)2]+ and [H(O=CHCH3)x]+ (x = 1 or 2), were isolated and characterized in the solid state for the first time. NBO analyses were used to quantify the increase in electrophilicity of the oxonium cations. The AsF5·O=R (R = C(CH3)2, C5H8, C10H14) adducts were synthesized and characterized in solution and solid state using LT NMR and Raman spectroscopies, respectively."],"dc:identifier":["hdl:10133/5195"],"dc:subject":["Organofluorine compounds","Sulfur tetrafluoride","Carbonyl compounds","Lewis acids","deoxofluorination reactions","Lewis acid-base reactions","organic carbonyl compounds","organofluorine chemistry"],"dc:title":["A study of proposed intermediates in the deoxofluorination of carbonyl groups by SF4"],"dc:type":["Thesis"]},"updated_at":"2026-07-27T20:02:41Z"}