Exploratory and mechanistic phenylallene photochemistry: protic solvent additions, isomerizations, and reactions of photogenerated radical cations

dc.contributor.author Klett, Michael
dc.contributor.department Chemistry
dc.date 2018-08-17T08:45:59.000
dc.date.accessioned 2020-07-02T06:04:12Z
dc.date.available 2020-07-02T06:04:12Z
dc.date.copyright Wed Jan 01 00:00:00 UTC 1986
dc.date.issued 1986
dc.description.abstract <p>Exploratory and mechanistic photochemistry of tetraphenyl-, triphenyl-, diphenyl- and phenyl-allene are described in alcohol and hydrocarbon solvents. Phenylallene singlet excited states yield predominantly allylic methyl ethers in methanol. A high stereoselectivity and deuterium isotope effect observed for product formation strongly argue for a rate determining protonation and fast methoxide trapping in an effectively concerted manner. By contrast, phenylallenes undergo photoisomerization to cyclopropenes, indenes and propynes in hydrocarbon solvents. The common, but not exclusive, intermediacy of vinyl-carbenes in allene and cyclopropene photochemistry is strongly indicated by product studies, independent generation and deuterium isotope effects. Reactions of photogenerated radical cations of tetraphenyl- and triphenyl-allene and triphenylpropyne in methanol are described. Allene radical cations yield vinyl methyl ethers as the major products whereas the predominant pathway for the propyne radical cations is efficient deprotonation-reprotonation to allene.</p>
dc.format.mimetype application/pdf
dc.identifier archive/lib.dr.iastate.edu/rtd/8011/
dc.identifier.articleid 9010
dc.identifier.contextkey 6328603
dc.identifier.doi https://doi.org/10.31274/rtd-180813-5734
dc.identifier.s3bucket isulib-bepress-aws-west
dc.identifier.submissionpath rtd/8011
dc.identifier.uri https://dr.lib.iastate.edu/handle/20.500.12876/80953
dc.language.iso en
dc.source.bitstream archive/lib.dr.iastate.edu/rtd/8011/r_8615059.pdf|||Sat Jan 15 02:05:08 UTC 2022
dc.subject.disciplines Organic Chemistry
dc.subject.keywords Chemistry
dc.subject.keywords Chemistry
dc.subject.keywords Organic
dc.title Exploratory and mechanistic phenylallene photochemistry: protic solvent additions, isomerizations, and reactions of photogenerated 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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