Structural and spectroscopic studies with dithizone and its derivatives

 

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dc.contributor.advisor Irving, H M N H en_ZA
dc.contributor.author Hutton, Alan T en_ZA
dc.date.accessioned 2015-06-25T13:48:35Z
dc.date.available 2015-06-25T13:48:35Z
dc.date.issued 1980 en_ZA
dc.identifier.citation Hutton, A. 1980. Structural and spectroscopic studies with dithizone and its derivatives. University of Cape Town. en_ZA
dc.identifier.uri http://hdl.handle.net/11427/13104
dc.description Bibliography: p. 262-274. en_ZA
dc.description.abstract 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. en_ZA
dc.language.iso eng en_ZA
dc.subject.other Analytical Science en_ZA
dc.title Structural and spectroscopic studies with dithizone and its derivatives en_ZA
dc.type Doctoral Thesis
uct.type.publication Research en_ZA
uct.type.resource Thesis en_ZA
dc.publisher.institution University of Cape Town
dc.publisher.faculty Faculty of Science en_ZA
dc.publisher.department Department of Physics en_ZA
dc.type.qualificationlevel Doctoral
dc.type.qualificationname PhD en_ZA
uct.type.filetype Text
uct.type.filetype Image
dc.identifier.apacitation Hutton, 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/11427/13104 en_ZA
dc.identifier.chicagocitation Hutton, 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/11427/13104 en_ZA
dc.identifier.vancouvercitation Hutton 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/11427/13104 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


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