{"id":{"repo_id":"vt","oai_identifier":"oai:vtechworks.lib.vt.edu:10919/88688"},"canonical_url":"https://search.dev.ndltd.org/etd/vt/oai:vtechworks.lib.vt.edu:10919/88688","repository":{"repo_id":"vt","name":"Virginia Tech","base_url":"https://vtechworks.lib.vt.edu/oai/request"},"display":{"title":"Fluorosulfanylimination including related reactions and structural problems and thiazyl trifluoride complexes of the transition metals","abstract":"This thesis reports the preparation of new pentafluorosulfanylimino (SF₅N=) derivatives, which have been synthesized from pentafluorosulfanyl isocyanate, SF₅NCO, pentafluorosulfanylamine, SF₅NH₂, and pentafluorosulfanyliminosulfur difluoride, SF₅N=SF₂. Reactions of SF₅NCO, SF₅N=SF₂, and SF₅NH₂, with appropriate substrates have produced SFN=S(CH₃)₂, SF₅N=CHC₆H₅, SF₅N=SCl₂, (SF5N=)₂C, (SF5N=)₂S and SF₅N=PCl₃, some of which are new compounds and some of which represent improved routes to compounds previously reported. When N,N'-bis(pentafluorosulfanyl)urea, (SF₅NH)₂CO, reacted with carbonyl fluoride SF₅NCO was formed. The reactivity of SF₅NCO in several basic reaction types including nucleophilic substitution, addition, exchange and coupling reactions was examined. Pentafluorosulfanyl isocyanate and dimethyl sulfoxide reacted to produce a crystalline product identified by its H-1 and F-19 nmr and in spectra as SF₅N-S(CH₃)₂. Pentafluorosulfanyl isocyanate and benzaldehyde reacted to produce a yellow solution and carbon dioxide. The solution was determined by spectroscopic mean to contain SF₅N=CHC₆H₅, a novel, electron-deficient Schiff base. Pentafluorosulfanylisocyanate and PCl5 reacted readily at 60-80° producing SF₅N=CCl₂ and POCl₃. A slow reaction between SF₅NCO and excess AgF₂ took place at room temperature. Infrared analysis of the reaction mixture at increasing temperatures gave evidence for formation and subsequent decomposition ofSF₅N=NSF₅. Pentafluorosulfanyliminosulfur difluoride (obtained from irradiation of N≡SF₃) reacted at room temperature with PCl₅ to produce SF₅N=SCl₂, a pale yellow liquid which rapidly attacked mercury, and reacted with AgF₂ (producing SF₅N=SF₂) and with SF₅NH₂(producing SF₅N=S=NSF₅). Pentafluorosulfanylamine, SF₅NH₂, and PCl₅ reacted at room temperature to give SF₅N=PCl₃ a pale yellow liquid which reacted rapidly with mercury. Thiazyl trifluoride reacted with metal carbonyls (Ni(Co)₄ , Fe(CO)₅, Mo(CO)₆, Mn(CO)₆) and ferrocene to produce thiazyl trifluoride - transition metal complexes. Chemical similarities between SF₅NCO and SF₅N=SF₂ with respect to nucleophilic substitution, exchange and coupling reaction reflect the similarity in bonding expected in these two systems. However, the failure of SF₅N=SF₂ and compounds containing the -N=SF₂ group to undergo additional reactions with polar reagents indicates some gross discrepancy from the usual behavior of these multiply bonded systems. Thus, a theoretical study of -N=SF₂ system was undertaken to clarify the role and magnitude of d-orbitals in the bonding of -N=SF₂ compounds. Theoretical calculations (CNDO) of the total energy of SF₅N=SF₂ , CF3N=SF₂ , C₂ F₅N=SF₂ , and FCON=SF₂ as a function of rotation about the N-S(IV) multiple bond showed that each total energy curve possessed a broad, flat minimum. Rotamers derived with only slight excitation would possess equal energy. Therefore, this multiple bond is nonrigid in contrast to the usual concept of the pπ-pπ double bond. The d-orbital contribution accounts for approximately 50% of the total π-bonding and is practically independent of the nature of the substituents on the nitrogen atom. Low temperature F-19 nmr studies showed that splittings occurred which can be explained on the basis of the total energy curves derived from the calculations.","abstract_html":"This thesis reports the preparation of new pentafluorosulfanylimino (SF₅N=) derivatives, which have been synthesized from pentafluorosulfanyl isocyanate, SF₅NCO, pentafluorosulfanylamine, SF₅NH₂, and pentafluorosulfanyliminosulfur difluoride, SF₅N=SF₂. Reactions of SF₅NCO, SF₅N=SF₂, and SF₅NH₂, with appropriate substrates have produced SFN=S(CH₃)₂, SF₅N=CHC₆H₅, SF₅N=SCl₂, (SF5N=)₂C, (SF5N=)₂S and SF₅N=PCl₃, some of which are new compounds and some of which represent improved routes to compounds previously reported. When N,N'-bis(pentafluorosulfanyl)urea, (SF₅NH)₂CO, reacted with carbonyl fluoride SF₅NCO was formed. The reactivity of SF₅NCO in several basic reaction types including nucleophilic substitution, addition, exchange and coupling reactions was examined. Pentafluorosulfanyl isocyanate and dimethyl sulfoxide reacted to produce a crystalline product identified by its H-1 and F-19 nmr and in spectra as SF₅N-S(CH₃)₂. Pentafluorosulfanyl isocyanate and benzaldehyde reacted to produce a yellow solution and carbon dioxide. The solution was determined by spectroscopic mean to contain SF₅N=CHC₆H₅, a novel, electron-deficient Schiff base. Pentafluorosulfanylisocyanate and PCl5 reacted readily at 60-80° producing SF₅N=CCl₂ and POCl₃. A slow reaction between SF₅NCO and excess AgF₂ took place at room temperature. Infrared analysis of the reaction mixture at increasing temperatures gave evidence for formation and subsequent decomposition ofSF₅N=NSF₅. Pentafluorosulfanyliminosulfur difluoride (obtained from irradiation of N≡SF₃) reacted at room temperature with PCl₅ to produce SF₅N=SCl₂, a pale yellow liquid which rapidly attacked mercury, and reacted with AgF₂ (producing SF₅N=SF₂) and with SF₅NH₂(producing SF₅N=S=NSF₅). Pentafluorosulfanylamine, SF₅NH₂, and PCl₅ reacted at room temperature to give SF₅N=PCl₃ a pale yellow liquid which reacted rapidly with mercury. Thiazyl trifluoride reacted with metal carbonyls (Ni(Co)₄ , Fe(CO)₅, Mo(CO)₆, Mn(CO)₆) and ferrocene to produce thiazyl trifluoride - transition metal complexes. Chemical similarities between SF₅NCO and SF₅N=SF₂ with respect to nucleophilic substitution, exchange and coupling reaction reflect the similarity in bonding expected in these two systems. However, the failure of SF₅N=SF₂ and compounds containing the -N=SF₂ group to undergo additional reactions with polar reagents indicates some gross discrepancy from the usual behavior of these multiply bonded systems. Thus, a theoretical study of -N=SF₂ system was undertaken to clarify the role and magnitude of d-orbitals in the bonding of -N=SF₂ compounds. Theoretical calculations (CNDO) of the total energy of SF₅N=SF₂ , CF3N=SF₂ , C₂ F₅N=SF₂ , and FCON=SF₂ as a function of rotation about the N-S(IV) multiple bond showed that each total energy curve possessed a broad, flat minimum. Rotamers derived with only slight excitation would possess equal energy. Therefore, this multiple bond is nonrigid in contrast to the usual concept of the pπ-pπ double bond. The d-orbital contribution accounts for approximately 50% of the total π-bonding and is practically independent of the nature of the substituents on the nitrogen atom. Low temperature F-19 nmr studies showed that splittings occurred which can be explained on the basis of the total energy curves derived from the calculations.","abstract_has_math":false,"creators":["Shanzer, Abraham"],"institution":"Virginia Polytechnic Institute and State University","degree_name":"Doctor of Philosophy","degree_level":"doctoral","degree_discipline":null,"degree_department":"Chemistry","school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":1976,"date_issued":"1976","date_published":"1976","updated_at":"2026-07-22T22:19:03Z","subjects":[],"languages":["en"],"rights":["In Copyright"],"rights_urls":["http://rightsstatements.org/vocab/InC/1.0/"],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/10919/88688","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.department","label":"Department","values":["Chemistry"]},{"key":"dc:creator","label":"Author","values":["Shanzer, Abraham"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2019-03-26T19:53:21Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2019-03-26T19:53:21Z"]},{"key":"dc:date.issued","label":"Date","values":["1976"]},{"key":"dc:publisher","label":"Institution","values":["Virginia Polytechnic Institute and State University"]},{"key":"dc:type","label":"Dc Type","values":["Dissertation"]},{"key":"dc:type.dcmitype","label":"Dc Type Dcmitype","values":["Text"]},{"key":"thesis:degree_level","label":"Degree Level","values":["doctoral"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Doctor of Philosophy"]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["Virginia Polytechnic Institute and State University"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language.iso","label":"Language (ISO)","values":["en"]},{"key":"dc:rights","label":"Dc Rights","values":["In Copyright"]},{"key":"dc:rights.uri","label":"Rights URI","values":["http://rightsstatements.org/vocab/InC/1.0/"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["http://hdl.handle.net/10919/88688"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["This thesis reports the preparation of new pentafluorosulfanylimino (SF₅N=) derivatives, which have been synthesized from pentafluorosulfanyl isocyanate, SF₅NCO, pentafluorosulfanylamine, SF₅NH₂, and pentafluorosulfanyliminosulfur difluoride, SF₅N=SF₂. Reactions of SF₅NCO, SF₅N=SF₂, and SF₅NH₂, with appropriate substrates have produced SFN=S(CH₃)₂, SF₅N=CHC₆H₅, SF₅N=SCl₂, (SF5N=)₂C, (SF5N=)₂S and SF₅N=PCl₃, some of which are new compounds and some of which represent improved routes to compounds previously reported. When N,N'-bis(pentafluorosulfanyl)urea, (SF₅NH)₂CO, reacted with carbonyl fluoride SF₅NCO was formed. The reactivity of SF₅NCO in several basic reaction types including nucleophilic substitution, addition, exchange and coupling reactions was examined. Pentafluorosulfanyl isocyanate and dimethyl sulfoxide reacted to produce a crystalline product identified by its H-1 and F-19 nmr and in spectra as SF₅N-S(CH₃)₂. Pentafluorosulfanyl isocyanate and benzaldehyde reacted to produce a yellow solution and carbon dioxide. The solution was determined by spectroscopic mean to contain SF₅N=CHC₆H₅, a novel, electron-deficient Schiff base. Pentafluorosulfanylisocyanate and PCl5 reacted readily at 60-80° producing SF₅N=CCl₂ and POCl₃. A slow reaction between SF₅NCO and excess AgF₂ took place at room temperature. Infrared analysis of the reaction mixture at increasing temperatures gave evidence for formation and subsequent decomposition ofSF₅N=NSF₅. Pentafluorosulfanyliminosulfur difluoride (obtained from irradiation of N≡SF₃) reacted at room temperature with PCl₅ to produce SF₅N=SCl₂, a pale yellow liquid which rapidly attacked mercury, and reacted with AgF₂ (producing SF₅N=SF₂) and with SF₅NH₂(producing SF₅N=S=NSF₅). Pentafluorosulfanylamine, SF₅NH₂, and PCl₅ reacted at room temperature to give SF₅N=PCl₃ a pale yellow liquid which reacted rapidly with mercury. Thiazyl trifluoride reacted with metal carbonyls (Ni(Co)₄ , Fe(CO)₅, Mo(CO)₆, Mn(CO)₆) and ferrocene to produce thiazyl trifluoride - transition metal complexes. Chemical similarities between SF₅NCO and SF₅N=SF₂ with respect to nucleophilic substitution, exchange and coupling reaction reflect the similarity in bonding expected in these two systems. However, the failure of SF₅N=SF₂ and compounds containing the -N=SF₂ group to undergo additional reactions with polar reagents indicates some gross discrepancy from the usual behavior of these multiply bonded systems. Thus, a theoretical study of -N=SF₂ system was undertaken to clarify the role and magnitude of d-orbitals in the bonding of -N=SF₂ compounds. Theoretical calculations (CNDO) of the total energy of SF₅N=SF₂ , CF3N=SF₂ , C₂ F₅N=SF₂ , and FCON=SF₂ as a function of rotation about the N-S(IV) multiple bond showed that each total energy curve possessed a broad, flat minimum. Rotamers derived with only slight excitation would possess equal energy. Therefore, this multiple bond is nonrigid in contrast to the usual concept of the pπ-pπ double bond. The d-orbital contribution accounts for approximately 50% of the total π-bonding and is practically independent of the nature of the substituents on the nitrogen atom. Low temperature F-19 nmr studies showed that splittings occurred which can be explained on the basis of the total energy curves derived from the calculations."]},{"key":"dc:description.degree","label":"Dc Description Degree","values":["Doctor of Philosophy"]},{"key":"dc:format.mimetype","label":"Dc Format Mimetype","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["Fluorosulfanylimination including related reactions and structural problems and thiazyl trifluoride complexes of the transition metals"]}]}],"canonical_facts":{"dc:contributor.department":["Chemistry"],"dc:creator":["Shanzer, Abraham"],"dc:date.accessioned":["2019-03-26T19:53:21Z"],"dc:date.available":["2019-03-26T19:53:21Z"],"dc:date.issued":["1976"],"dc:description.abstract":["This thesis reports the preparation of new pentafluorosulfanylimino (SF₅N=) derivatives, which have been synthesized from pentafluorosulfanyl isocyanate, SF₅NCO, pentafluorosulfanylamine, SF₅NH₂, and pentafluorosulfanyliminosulfur difluoride, SF₅N=SF₂. Reactions of SF₅NCO, SF₅N=SF₂, and SF₅NH₂, with appropriate substrates have produced SFN=S(CH₃)₂, SF₅N=CHC₆H₅, SF₅N=SCl₂, (SF5N=)₂C, (SF5N=)₂S and SF₅N=PCl₃, some of which are new compounds and some of which represent improved routes to compounds previously reported. When N,N'-bis(pentafluorosulfanyl)urea, (SF₅NH)₂CO, reacted with carbonyl fluoride SF₅NCO was formed. The reactivity of SF₅NCO in several basic reaction types including nucleophilic substitution, addition, exchange and coupling reactions was examined. Pentafluorosulfanyl isocyanate and dimethyl sulfoxide reacted to produce a crystalline product identified by its H-1 and F-19 nmr and in spectra as SF₅N-S(CH₃)₂. Pentafluorosulfanyl isocyanate and benzaldehyde reacted to produce a yellow solution and carbon dioxide. The solution was determined by spectroscopic mean to contain SF₅N=CHC₆H₅, a novel, electron-deficient Schiff base. Pentafluorosulfanylisocyanate and PCl5 reacted readily at 60-80° producing SF₅N=CCl₂ and POCl₃. A slow reaction between SF₅NCO and excess AgF₂ took place at room temperature. Infrared analysis of the reaction mixture at increasing temperatures gave evidence for formation and subsequent decomposition ofSF₅N=NSF₅. Pentafluorosulfanyliminosulfur difluoride (obtained from irradiation of N≡SF₃) reacted at room temperature with PCl₅ to produce SF₅N=SCl₂, a pale yellow liquid which rapidly attacked mercury, and reacted with AgF₂ (producing SF₅N=SF₂) and with SF₅NH₂(producing SF₅N=S=NSF₅). Pentafluorosulfanylamine, SF₅NH₂, and PCl₅ reacted at room temperature to give SF₅N=PCl₃ a pale yellow liquid which reacted rapidly with mercury. Thiazyl trifluoride reacted with metal carbonyls (Ni(Co)₄ , Fe(CO)₅, Mo(CO)₆, Mn(CO)₆) and ferrocene to produce thiazyl trifluoride - transition metal complexes. Chemical similarities between SF₅NCO and SF₅N=SF₂ with respect to nucleophilic substitution, exchange and coupling reaction reflect the similarity in bonding expected in these two systems. However, the failure of SF₅N=SF₂ and compounds containing the -N=SF₂ group to undergo additional reactions with polar reagents indicates some gross discrepancy from the usual behavior of these multiply bonded systems. Thus, a theoretical study of -N=SF₂ system was undertaken to clarify the role and magnitude of d-orbitals in the bonding of -N=SF₂ compounds. Theoretical calculations (CNDO) of the total energy of SF₅N=SF₂ , CF3N=SF₂ , C₂ F₅N=SF₂ , and FCON=SF₂ as a function of rotation about the N-S(IV) multiple bond showed that each total energy curve possessed a broad, flat minimum. Rotamers derived with only slight excitation would possess equal energy. Therefore, this multiple bond is nonrigid in contrast to the usual concept of the pπ-pπ double bond. The d-orbital contribution accounts for approximately 50% of the total π-bonding and is practically independent of the nature of the substituents on the nitrogen atom. Low temperature F-19 nmr studies showed that splittings occurred which can be explained on the basis of the total energy curves derived from the calculations."],"dc:description.degree":["Doctor of Philosophy"],"dc:format.mimetype":["application/pdf"],"dc:identifier.uri":["http://hdl.handle.net/10919/88688"],"dc:language.iso":["en"],"dc:publisher":["Virginia Polytechnic Institute and State University"],"dc:rights":["In Copyright"],"dc:rights.uri":["http://rightsstatements.org/vocab/InC/1.0/"],"dc:title":["Fluorosulfanylimination including related reactions and structural problems and thiazyl trifluoride complexes of the transition metals"],"dc:type":["Dissertation"],"dc:type.dcmitype":["Text"],"thesis:degree_level":["doctoral"],"thesis:degree_name":["Doctor of Philosophy"],"thesis:institution_name":["Virginia Polytechnic Institute and State University"]},"updated_at":"2026-07-22T22:19:03Z"}