Synthesis and electron spin resonance spectroscopy of organo-sulfur radical cations

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dc.contributor.author Law, Wing
dc.contributor.department Chemistry
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.copyright Wed Jan 01 00:00:00 UTC 1986
dc.date.issued 1986
dc.description.abstract <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>
dc.format.mimetype application/pdf
dc.identifier archive/lib.dr.iastate.edu/rtd/8014/
dc.identifier.articleid 9013
dc.identifier.contextkey 6328614
dc.identifier.doi https://doi.org/10.31274/rtd-180813-5736
dc.identifier.s3bucket isulib-bepress-aws-west
dc.identifier.submissionpath rtd/8014
dc.identifier.uri https://dr.lib.iastate.edu/handle/20.500.12876/80956
dc.language.iso en
dc.source.bitstream archive/lib.dr.iastate.edu/rtd/8014/r_8615062.pdf|||Sat Jan 15 02:05:09 UTC 2022
dc.subject.disciplines Organic Chemistry
dc.subject.keywords Chemistry
dc.subject.keywords Chemistry
dc.subject.keywords Organic
dc.title Synthesis and electron spin resonance spectroscopy of organo-sulfur radical cations
dc.type article
dc.type.genre dissertation
dspace.entity.type Publication
relation.isOrgUnitOfPublication 42864f6e-7a3d-4be3-8b5a-0ae3c3830a11
thesis.degree.level dissertation
thesis.degree.name Doctor of Philosophy
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