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Synthetic studies into phosphorus and arsenic peri-substituted naphthalene
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dc.contributor.advisor | Kilian, Petr | |
dc.contributor.author | Somisara, Dhanasekara M. U. K. | |
dc.coverage.spatial | 221 | en_US |
dc.date.accessioned | 2012-09-20T20:40:36Z | |
dc.date.available | 2012-09-20T20:40:36Z | |
dc.date.issued | 2011-06-08 | |
dc.identifier | uk.bl.ethos.556359 | |
dc.identifier.uri | https://hdl.handle.net/10023/3106 | |
dc.description.abstract | The rac- and meso- forms of “all carbon” 1,2-diphosphonium dications with the naphthalene -1,8-diyl backbone were synthesised in good yields and purity by double alkylation of the parent diphosphine (1,2-diphenyl-1,2-diphosphaacenaphthene) using strong alkylating agents. Pure rac- and meso- forms of 1,2-diphosphoniums were obtained diastereospecifically by using methyl triflate and trimethyloxonium tetrafluoroborate respectively. It was found that the equilibrium between the rac- and meso- forms at room temperature in acetonitrile solutions effectively depends on the anion present. A reaction mechanism which proceeds via a P-pentacoordinated intermediate was proposed for the epimerisation observed between the rac- and meso- forms in the presence of F⁻ donors in the solution. Reactivity of the new 1,2-dications towards a range of compounds (nucleophiles, bases) was examined and a series of new compounds including phosphine-phosphoniums and phosphonium-phosphine oxides were obtained. Cyclic and acyclic compounds belonging to a novel group of phosphine-arsine mixed peri-substituted acenaphthenes were synthesised by introducing arsenic and phosphorus to the acenaphthene ring, using stepwise lithiation and carbon-group 15 element coupling. All new compounds were fully characterised including single crystal X-ray diffraction. The effect of the peri-substitution by phosphorus moieties and mixed arsine-phosphine peri-substitution on the naphthalene ring was studied using the detailed structural data obtained for these systems. | en_US |
dc.language.iso | en | en_US |
dc.publisher | University of St Andrews | |
dc.subject | 1,2-diphosphonium dications | en_US |
dc.subject | Peri-substitution | en_US |
dc.subject | Phosphine-arsine | en_US |
dc.subject.lcc | QD391.S7 | |
dc.subject.lcsh | Naphthalene | en_US |
dc.subject.lcsh | Organophosphorus compounds | en_US |
dc.subject.lcsh | Organoarsenic compounds | en_US |
dc.title | Synthetic studies into phosphorus and arsenic peri-substituted naphthalene | en_US |
dc.type | Thesis | en_US |
dc.contributor.sponsor | EaStCHEM | en_US |
dc.type.qualificationlevel | Doctoral | en_US |
dc.type.qualificationname | PhD Doctor of Philosophy | en_US |
dc.publisher.institution | The University of St Andrews | en_US |
dc.rights.embargodate | Print and electronic copy restricted until 20th June 2018 | en_US |
dc.rights.embargoreason | Thesis restricted in accordance with University regulations | en_US |
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