Structural and spectroscopic studies with dithizone and its derivatives

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dc.contributor.advisorIrving, H M N Hen_ZA
dc.contributor.authorHutton, Alan Ten_ZA
dc.date.accessioned2015-06-25T13:48:35Z
dc.date.available2015-06-25T13:48:35Z
dc.date.issued1980en_ZA
dc.descriptionBibliography: p. 262-274.en_ZA
dc.description.abstractAn X-ray crystal structure detennination of 3-nitro-l,5-di(2,6-dimethylphenyl) fonnazan, ArN:N•C(N02):N•NHAr (Ar= 2,6-dimethylphenyl), has shown that the N-N-C-N-N chain is stabilized by an unusual hydrogen bond in the closed-ring syn,s-cis configuration relative to the formal double C=N and single C-N bonds. The bond lengths reveal complete n-electron delocalization along the chain which results in a mesomeric structure; the possibility of such a mesomeric structure existing in solution rather than a rapid tautomeric equilibrium between two limiting forms of the resonance hybrid has been considered in the light of i.r. and n.m.r. spectroscopic measurements. The temporal changes in the visible absorption spectrum of S-methyldithizone, PhN:N•C(SCH3):N•NHPh, have been shown to arise from syn-anti isomerization about the fonnal C=N double bond and rotation about the C-N single bond by considering the evidence provided by i. r. and n.m.r. spectroscopic studies combined with the X-ray crystal structure of the di(o-tolyl) homologue. The parent compound dithizone, PhN:N•C(SH):N•NHPh, previously thought to exist as an equilibritim of thiol and thione forms in solution has now been shown to consist of a single species in solution mainly by consideration of its n.m.r. spectroscopic properties. Organomercury(II) complexes of dithizone have been shown to be photochromic in solution; X-ray crystal structure detenninations of phenyland methylmercury(II) dithizonate, besides revealing rare three-coordination of mercury, have been combined with spectroscopic measurements on the normal and activated fonns to reveal the structure of the labile photo-isomers.en_ZA
dc.identifier.apacitationHutton, A. T. (1980). <i>Structural and spectroscopic studies with dithizone and its derivatives</i>. (Thesis). University of Cape Town ,Faculty of Science ,Department of Physics. Retrieved from http://hdl.handle.net/11427/13104en_ZA
dc.identifier.chicagocitationHutton, Alan T. <i>"Structural and spectroscopic studies with dithizone and its derivatives."</i> Thesis., University of Cape Town ,Faculty of Science ,Department of Physics, 1980. http://hdl.handle.net/11427/13104en_ZA
dc.identifier.citationHutton, A. 1980. Structural and spectroscopic studies with dithizone and its derivatives. University of Cape Town.en_ZA
dc.identifier.ris TY - Thesis / Dissertation AU - Hutton, Alan T AB - An X-ray crystal structure detennination of 3-nitro-l,5-di(2,6-dimethylphenyl) fonnazan, ArN:N•C(N02):N•NHAr (Ar= 2,6-dimethylphenyl), has shown that the N-N-C-N-N chain is stabilized by an unusual hydrogen bond in the closed-ring syn,s-cis configuration relative to the formal double C=N and single C-N bonds. The bond lengths reveal complete n-electron delocalization along the chain which results in a mesomeric structure; the possibility of such a mesomeric structure existing in solution rather than a rapid tautomeric equilibrium between two limiting forms of the resonance hybrid has been considered in the light of i.r. and n.m.r. spectroscopic measurements. The temporal changes in the visible absorption spectrum of S-methyldithizone, PhN:N•C(SCH3):N•NHPh, have been shown to arise from syn-anti isomerization about the fonnal C=N double bond and rotation about the C-N single bond by considering the evidence provided by i. r. and n.m.r. spectroscopic studies combined with the X-ray crystal structure of the di(o-tolyl) homologue. The parent compound dithizone, PhN:N•C(SH):N•NHPh, previously thought to exist as an equilibritim of thiol and thione forms in solution has now been shown to consist of a single species in solution mainly by consideration of its n.m.r. spectroscopic properties. Organomercury(II) complexes of dithizone have been shown to be photochromic in solution; X-ray crystal structure detenninations of phenyland methylmercury(II) dithizonate, besides revealing rare three-coordination of mercury, have been combined with spectroscopic measurements on the normal and activated fonns to reveal the structure of the labile photo-isomers. DA - 1980 DB - OpenUCT DP - University of Cape Town LK - https://open.uct.ac.za PB - University of Cape Town PY - 1980 T1 - Structural and spectroscopic studies with dithizone and its derivatives TI - Structural and spectroscopic studies with dithizone and its derivatives UR - http://hdl.handle.net/11427/13104 ER - en_ZA
dc.identifier.urihttp://hdl.handle.net/11427/13104
dc.identifier.vancouvercitationHutton AT. Structural and spectroscopic studies with dithizone and its derivatives. [Thesis]. University of Cape Town ,Faculty of Science ,Department of Physics, 1980 [cited yyyy month dd]. Available from: http://hdl.handle.net/11427/13104en_ZA
dc.language.isoengen_ZA
dc.publisher.departmentDepartment of Physicsen_ZA
dc.publisher.facultyFaculty of Scienceen_ZA
dc.publisher.institutionUniversity of Cape Town
dc.subject.otherAnalytical Scienceen_ZA
dc.titleStructural and spectroscopic studies with dithizone and its derivativesen_ZA
dc.typeDoctoral Thesis
dc.type.qualificationlevelDoctoral
dc.type.qualificationnamePhDen_ZA
uct.type.filetypeText
uct.type.filetypeImage
uct.type.publicationResearchen_ZA
uct.type.resourceThesisen_ZA
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