Syntheses of selected mono- and di-esters of phosphoric acid and stability constants of their copper (II) complexes

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dc.contributor.advisorModro, Tomasz Aen_ZA
dc.contributor.advisorLinder, P Wen_ZA
dc.contributor.advisorTorrington, R Gen_ZA
dc.contributor.authorArmstrong, Moira Margareten_ZA
dc.date.accessioned2016-02-15T07:16:01Z
dc.date.available2016-02-15T07:16:01Z
dc.date.issued1984en_ZA
dc.descriptionBibliography: pages 109-113.en_ZA
dc.description.abstractA number of different routes were attempted to the syntheses of organic phosphate models (R₁O)(R₂O)PO; where R₁ = 4-nitrophenyl group and R₂ = benzyl, 2-pyridylmethyl, 1-naphthylor 8-quinolyl group. However, preparative difficulties and side reactions, due mainly to the susceptibility of the 4-nitrophenoxy moiety to nucleophilic displacement reactions, resulted in simplification of the target models to a pair of monoesters (R₃O)PO₃H₂ and a pair of diesters (R₃O)(R₄O)P(O)O⁻Na⁺ where R₃ = 1-naphthyl group (monoester (A) or diester (C)) or 8-quinolyl group (monoester (B) or diester (D)) and R₄ = methyl group. Such a set of substrates allowed comparison of the reactivities of phosphate monoesters and diesters and as the components of each pair differed only by the presence or absence of a tertiary amine function in one of the ester linkages, the effect on the reactivity of such a compound, due to the presence of a heterocyclic atom, could be gauged. Complex formation between ligands (A), (B), (C) and (D) and copper(II) ions in aqueous solution at 25° C and I = 0,15 mol dm⁻³ (Na)[Cl⁻] was investigated by means of glass electrode potentiometry and computational analysis. Mononuclear and hydroxo complexes were found to occur with ligands (A), (B) and (D). No complexation was detected with ligand (C). The copper(II) ion was found to be only singly coordinated to ligands (A) and (D) through a terminal phosphate group and the quinolyl nitrogen respectively,while with ligand (B) a chelate structure was formed involving the quinolyl nitrogen and a terminal phosphate group to form a seven-membered ring. Formation constants are given for two protonation and four copper(II) complexes of ligand (B) and for one protonation and four copper(II) complexes, each, of ligands (A) and (D).en_ZA
dc.identifier.apacitationArmstrong, M. M. (1984). <i>Syntheses of selected mono- and di-esters of phosphoric acid and stability constants of their copper (II) complexes</i>. (Thesis). University of Cape Town ,Faculty of Science ,Department of Chemistry. Retrieved from http://hdl.handle.net/11427/17044en_ZA
dc.identifier.chicagocitationArmstrong, Moira Margaret. <i>"Syntheses of selected mono- and di-esters of phosphoric acid and stability constants of their copper (II) complexes."</i> Thesis., University of Cape Town ,Faculty of Science ,Department of Chemistry, 1984. http://hdl.handle.net/11427/17044en_ZA
dc.identifier.citationArmstrong, M. 1984. Syntheses of selected mono- and di-esters of phosphoric acid and stability constants of their copper (II) complexes. University of Cape Town.en_ZA
dc.identifier.ris TY - Thesis / Dissertation AU - Armstrong, Moira Margaret AB - A number of different routes were attempted to the syntheses of organic phosphate models (R₁O)(R₂O)PO; where R₁ = 4-nitrophenyl group and R₂ = benzyl, 2-pyridylmethyl, 1-naphthylor 8-quinolyl group. However, preparative difficulties and side reactions, due mainly to the susceptibility of the 4-nitrophenoxy moiety to nucleophilic displacement reactions, resulted in simplification of the target models to a pair of monoesters (R₃O)PO₃H₂ and a pair of diesters (R₃O)(R₄O)P(O)O⁻Na⁺ where R₃ = 1-naphthyl group (monoester (A) or diester (C)) or 8-quinolyl group (monoester (B) or diester (D)) and R₄ = methyl group. Such a set of substrates allowed comparison of the reactivities of phosphate monoesters and diesters and as the components of each pair differed only by the presence or absence of a tertiary amine function in one of the ester linkages, the effect on the reactivity of such a compound, due to the presence of a heterocyclic atom, could be gauged. Complex formation between ligands (A), (B), (C) and (D) and copper(II) ions in aqueous solution at 25° C and I = 0,15 mol dm⁻³ (Na)[Cl⁻] was investigated by means of glass electrode potentiometry and computational analysis. Mononuclear and hydroxo complexes were found to occur with ligands (A), (B) and (D). No complexation was detected with ligand (C). The copper(II) ion was found to be only singly coordinated to ligands (A) and (D) through a terminal phosphate group and the quinolyl nitrogen respectively,while with ligand (B) a chelate structure was formed involving the quinolyl nitrogen and a terminal phosphate group to form a seven-membered ring. Formation constants are given for two protonation and four copper(II) complexes of ligand (B) and for one protonation and four copper(II) complexes, each, of ligands (A) and (D). DA - 1984 DB - OpenUCT DP - University of Cape Town LK - https://open.uct.ac.za PB - University of Cape Town PY - 1984 T1 - Syntheses of selected mono- and di-esters of phosphoric acid and stability constants of their copper (II) complexes TI - Syntheses of selected mono- and di-esters of phosphoric acid and stability constants of their copper (II) complexes UR - http://hdl.handle.net/11427/17044 ER - en_ZA
dc.identifier.urihttp://hdl.handle.net/11427/17044
dc.identifier.vancouvercitationArmstrong MM. Syntheses of selected mono- and di-esters of phosphoric acid and stability constants of their copper (II) complexes. [Thesis]. University of Cape Town ,Faculty of Science ,Department of Chemistry, 1984 [cited yyyy month dd]. Available from: http://hdl.handle.net/11427/17044en_ZA
dc.language.isoengen_ZA
dc.publisher.departmentDepartment of Chemistryen_ZA
dc.publisher.facultyFaculty of Scienceen_ZA
dc.publisher.institutionUniversity of Cape Town
dc.subject.otherChemistryen_ZA
dc.titleSyntheses of selected mono- and di-esters of phosphoric acid and stability constants of their copper (II) complexesen_ZA
dc.typeMaster Thesis
dc.type.qualificationlevelMasters
dc.type.qualificationnameMScen_ZA
uct.type.filetypeText
uct.type.filetypeImage
uct.type.publicationResearchen_ZA
uct.type.resourceThesisen_ZA
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