A series of new radical cations in 1,4-dithiin, 1,4-benzodithiin, 2,3-dihydro-1,4-dithiin, 1,4-dithiepin, 1,2-dithietane, 1,2-dithiolane, 1,2-dithiane series were prepared. The SOMO of 1,4-dithiin, 1,4-benzodithiin, 2,3-dihydro-1,4-dithiin radical cations were found to be symmetrical while the SOMO of cyclic 1,2-disulfide radical cations were found to be antisymmetrical. 2,3-Dihydro-1,4-dithiin, 1,4-dithiepin radical cations were found to have conformational preference at low temperature and the activation parameters for the ring inversion processes were obtained. For 1,2-bis(isopropylthio)cyclohexene radical cation, the unusually low value of (DELTA)H('(NOT=)) for the cyclohexene ring inversion was explained by secondary interactions between the isopropyl groups and the (alpha) methylene groups. Sulfur-centered radical cations were found to be capable of showing sizable long range couplings in the radical cations of 2,5-dithiabicyclo 4.2.1 non-3-ene, 2,3-dithiabicyclo 2.2.1 heptane, 2,3-dithiabicyclo 2.2.2 octane. It is established from all the ESR results that the hfs of a hydrogen (beta) to a sulfur atom with spin density arises predominantly from angle-dependent hyperconjugation. For disulfide radical cations (not including 1,2-dithietane radical cations), a value of 35 G was calculated for the constant B which is a measure of the magnitude of this interaction. For 1,2-dithietane radical cations, a (sigma)-delocalized electronic structure for the 3-electron bond is proposed to explain the unusual conformational preference and the unusually low values of a('H);Sulfur-centered radical cations were generated by oxidative rearrangement. Thus, 2,2-dialkyl-1,3-dithiolanes rearranged to form 2,3-dihydro-1,4-dithiin radical cations when treated with either H(,2)SO(,4) or Al(,2)Cl(,6)/CH(,2)Cl(,2). Similarly, 2,3-dialkyl-1,3-benzodithioles rearranged to form the 1,4-benzodithiin radical cations. Diaryl disulfides underwent oxidative rearrangement to form benzodithiete and thianthrene radical cations. Methylbenzyl disulfides underwent oxidative rearrangement to form polymethylbenzodithiete and 2,6-dimethylanthrancene radical cations.
","abstract_html":"<p>A series of new radical cations in 1,4-dithiin, 1,4-benzodithiin, 2,3-dihydro-1,4-dithiin, 1,4-dithiepin, 1,2-dithietane, 1,2-dithiolane, 1,2-dithiane series were prepared. The SOMO of 1,4-dithiin, 1,4-benzodithiin, 2,3-dihydro-1,4-dithiin radical cations were found to be symmetrical while the SOMO of cyclic 1,2-disulfide radical cations were found to be antisymmetrical. 2,3-Dihydro-1,4-dithiin, 1,4-dithiepin radical cations were found to have conformational preference at low temperature and the activation parameters for the ring inversion processes were obtained. For 1,2-bis(isopropylthio)cyclohexene radical cation, the unusually low value of (DELTA)H('(NOT=)) for the cyclohexene ring inversion was explained by secondary interactions between the isopropyl groups and the (alpha) methylene groups. Sulfur-centered radical cations were found to be capable of showing sizable long range couplings in the radical cations of 2,5-dithiabicyclo 4.2.1 non-3-ene, 2,3-dithiabicyclo 2.2.1 heptane, 2,3-dithiabicyclo 2.2.2 octane. It is established from all the ESR results that the hfs of a hydrogen (beta) to a sulfur atom with spin density arises predominantly from angle-dependent hyperconjugation. For disulfide radical cations (not including 1,2-dithietane radical cations), a value of 35 G was calculated for the constant B which is a measure of the magnitude of this interaction. For 1,2-dithietane radical cations, a (sigma)-delocalized electronic structure for the 3-electron bond is proposed to explain the unusual conformational preference and the unusually low values of a('H);Sulfur-centered radical cations were generated by oxidative rearrangement. Thus, 2,2-dialkyl-1,3-dithiolanes rearranged to form 2,3-dihydro-1,4-dithiin radical cations when treated with either H(,2)SO(,4) or Al(,2)Cl(,6)/CH(,2)Cl(,2). Similarly, 2,3-dialkyl-1,3-benzodithioles rearranged to form the 1,4-benzodithiin radical cations. Diaryl disulfides underwent oxidative rearrangement to form benzodithiete and thianthrene radical cations. Methylbenzyl disulfides underwent oxidative rearrangement to form polymethylbenzodithiete and 2,6-dimethylanthrancene radical cations.</p>","abstract_has_math":false,"creators":["Law, Wing"],"institution":null,"degree_name":"Doctor of Philosophy","degree_level":"dissertation","degree_discipline":null,"degree_department":"Department of Chemistry","school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":1986,"date_issued":"1986","date_published":"1986","updated_at":"2026-07-24T02:37:27Z","subjects":[],"languages":["en"],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier.doi","label":"DOI","values":["https://doi.org/10.31274/rtd-180813-5736"],"render_values":[{"text":"https://doi.org/10.31274/rtd-180813-5736","href":"https://doi.org/10.31274/rtd-180813-5736","code":true}]},{"key":"dc:identifier","label":"Identifier","values":["archive/lib.dr.iastate.edu/rtd/8014/"],"render_values":[{"text":"archive/lib.dr.iastate.edu/rtd/8014/","href":null,"code":true}]}]},"links":{"outbound_url":"https://dr.lib.iastate.edu/handle/20.500.12876/80956","outbound_label":"Repository record","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.department","label":"Department","values":["Department of Chemistry"]},{"key":"dc:creator","label":"Author","values":["Law, Wing"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2018-08-17T11:17:35.000"]},{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2020-07-02T06:04:13Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2020-07-02T06:04:13Z"]},{"key":"dc:date.issued","label":"Date","values":["1986"]},{"key":"dc:type","label":"Dc Type","values":["dissertation"]},{"key":"thesis:degree_level","label":"Degree Level","values":["dissertation"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Doctor of Philosophy"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language.iso","label":"Language (ISO)","values":["en"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["archive/lib.dr.iastate.edu/rtd/8014/"]},{"key":"dc:identifier.doi","label":"DOI","values":["https://doi.org/10.31274/rtd-180813-5736"]},{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://dr.lib.iastate.edu/handle/20.500.12876/80956"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["A series of new radical cations in 1,4-dithiin, 1,4-benzodithiin, 2,3-dihydro-1,4-dithiin, 1,4-dithiepin, 1,2-dithietane, 1,2-dithiolane, 1,2-dithiane series were prepared. The SOMO of 1,4-dithiin, 1,4-benzodithiin, 2,3-dihydro-1,4-dithiin radical cations were found to be symmetrical while the SOMO of cyclic 1,2-disulfide radical cations were found to be antisymmetrical. 2,3-Dihydro-1,4-dithiin, 1,4-dithiepin radical cations were found to have conformational preference at low temperature and the activation parameters for the ring inversion processes were obtained. For 1,2-bis(isopropylthio)cyclohexene radical cation, the unusually low value of (DELTA)H('(NOT=)) for the cyclohexene ring inversion was explained by secondary interactions between the isopropyl groups and the (alpha) methylene groups. Sulfur-centered radical cations were found to be capable of showing sizable long range couplings in the radical cations of 2,5-dithiabicyclo 4.2.1 non-3-ene, 2,3-dithiabicyclo 2.2.1 heptane, 2,3-dithiabicyclo 2.2.2 octane. It is established from all the ESR results that the hfs of a hydrogen (beta) to a sulfur atom with spin density arises predominantly from angle-dependent hyperconjugation. For disulfide radical cations (not including 1,2-dithietane radical cations), a value of 35 G was calculated for the constant B which is a measure of the magnitude of this interaction. For 1,2-dithietane radical cations, a (sigma)-delocalized electronic structure for the 3-electron bond is proposed to explain the unusual conformational preference and the unusually low values of a('H);Sulfur-centered radical cations were generated by oxidative rearrangement. Thus, 2,2-dialkyl-1,3-dithiolanes rearranged to form 2,3-dihydro-1,4-dithiin radical cations when treated with either H(,2)SO(,4) or Al(,2)Cl(,6)/CH(,2)Cl(,2). Similarly, 2,3-dialkyl-1,3-benzodithioles rearranged to form the 1,4-benzodithiin radical cations. Diaryl disulfides underwent oxidative rearrangement to form benzodithiete and thianthrene radical cations. Methylbenzyl disulfides underwent oxidative rearrangement to form polymethylbenzodithiete and 2,6-dimethylanthrancene radical cations.
"]},{"key":"dc:format.mimetype","label":"Dc Format Mimetype","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["Synthesis and electron spin resonance spectroscopy of organo-sulfur radical cations"]}]}],"canonical_facts":{"dc:contributor.department":["Department of Chemistry"],"dc:creator":["Law, Wing"],"dc:date":["2018-08-17T11:17:35.000"],"dc:date.accessioned":["2020-07-02T06:04:13Z"],"dc:date.available":["2020-07-02T06:04:13Z"],"dc:date.issued":["1986"],"dc:description.abstract":["A series of new radical cations in 1,4-dithiin, 1,4-benzodithiin, 2,3-dihydro-1,4-dithiin, 1,4-dithiepin, 1,2-dithietane, 1,2-dithiolane, 1,2-dithiane series were prepared. The SOMO of 1,4-dithiin, 1,4-benzodithiin, 2,3-dihydro-1,4-dithiin radical cations were found to be symmetrical while the SOMO of cyclic 1,2-disulfide radical cations were found to be antisymmetrical. 2,3-Dihydro-1,4-dithiin, 1,4-dithiepin radical cations were found to have conformational preference at low temperature and the activation parameters for the ring inversion processes were obtained. For 1,2-bis(isopropylthio)cyclohexene radical cation, the unusually low value of (DELTA)H('(NOT=)) for the cyclohexene ring inversion was explained by secondary interactions between the isopropyl groups and the (alpha) methylene groups. Sulfur-centered radical cations were found to be capable of showing sizable long range couplings in the radical cations of 2,5-dithiabicyclo 4.2.1 non-3-ene, 2,3-dithiabicyclo 2.2.1 heptane, 2,3-dithiabicyclo 2.2.2 octane. It is established from all the ESR results that the hfs of a hydrogen (beta) to a sulfur atom with spin density arises predominantly from angle-dependent hyperconjugation. For disulfide radical cations (not including 1,2-dithietane radical cations), a value of 35 G was calculated for the constant B which is a measure of the magnitude of this interaction. For 1,2-dithietane radical cations, a (sigma)-delocalized electronic structure for the 3-electron bond is proposed to explain the unusual conformational preference and the unusually low values of a('H);Sulfur-centered radical cations were generated by oxidative rearrangement. Thus, 2,2-dialkyl-1,3-dithiolanes rearranged to form 2,3-dihydro-1,4-dithiin radical cations when treated with either H(,2)SO(,4) or Al(,2)Cl(,6)/CH(,2)Cl(,2). Similarly, 2,3-dialkyl-1,3-benzodithioles rearranged to form the 1,4-benzodithiin radical cations. Diaryl disulfides underwent oxidative rearrangement to form benzodithiete and thianthrene radical cations. Methylbenzyl disulfides underwent oxidative rearrangement to form polymethylbenzodithiete and 2,6-dimethylanthrancene radical cations.
"],"dc:format.mimetype":["application/pdf"],"dc:identifier":["archive/lib.dr.iastate.edu/rtd/8014/"],"dc:identifier.doi":["https://doi.org/10.31274/rtd-180813-5736"],"dc:identifier.uri":["https://dr.lib.iastate.edu/handle/20.500.12876/80956"],"dc:language.iso":["en"],"dc:title":["Synthesis and electron spin resonance spectroscopy of organo-sulfur radical cations"],"dc:type":["dissertation"],"thesis:degree_level":["dissertation"],"thesis:degree_name":["Doctor of Philosophy"]},"updated_at":"2026-07-24T02:37:27Z"}