Show simple item record

Files in this item

Thumbnail

Item metadata

dc.contributor.advisorWoollins, J. D. (J. Derek)
dc.contributor.advisorHey-Hawkins, E.
dc.contributor.authorGarland, Jacqueline M.
dc.coverage.spatial269en_US
dc.date.accessioned2013-06-13T10:37:16Z
dc.date.available2013-06-13T10:37:16Z
dc.date.issued2013-06-26
dc.identifieruk.bl.ethos.574795
dc.identifier.urihttps://hdl.handle.net/10023/3688
dc.description.abstractPhosphorus-selenium chemistry has seen a surge in development over the last five to ten years thanks to the optimisation of the synthesis of 2,4-diphenyl-1,3,2,4-diselenadiphosphetane-2,4-diselenide, Woollins’ Reagent. This selenium analogue of the well known Lawesson’s Reagent has proved itself to be a valuable asset to modern inorganic chemistry, providing a route to novel heterocycles, as well as acting as a selenation reagent with a wide range of functional groups. A series of new ammonium phenylphosphonamidodiselenoate ligands were synthesised via the reaction of Woollins’ Reagent with a range of amines. The products were obtained in high yields and could be used as ligands for the synthesis of novel metal complexes. The reaction of diisopropylamine N-isopropyl-P-phenylphosphonamidodiselenoate with nickel(II) acetate produces a dimeric structure, whilst the reaction with copper(II) acetate yields a beautiful cluster of the form Cu₆Se₃L₆. The phenylphosphonamidodiselenoate ligands were further reacted with a range of cis-Pt(PR₃)₂Cl₂ complexes to form a library of 20 novel compounds, which were studied by ³¹P{¹H}, ⁷⁷Se{¹H} and ¹⁹⁵Pt{¹H} NMR spectroscopy. The X-ray crystal structure of one of these compounds was obtained, which confirmed the atom connectivity and spatial arrangement of the complexes and the geometry around the platinum centre. During investigations into the above-mentioned platinum complexes, it was postulated that an increase in steric bulk of the phosphine ligands would aid crystallisation of the products. As such, trimesityl-, dimesitylphenyl- and mesityldiphenyl phosphine were synthesised and reacted with elemental sulfur and selenium and hydrogen peroxide, as well as Pt(cod)Cl₂ and K₂[PtCl₄], yielding nine new structures, all of which were characterised by X-ray crystallography, ³¹P{¹H}, ¹³C{¹H} and ¹H NMR spectroscopy. Finally Woollins’ Reagent was reacted directly with a selection of metal complexes, yielding some new insights into its reactivity with inorganic moieties, which has been relatively sparsely reported until now.en_US
dc.language.isoenen_US
dc.publisherUniversity of St Andrews
dc.subjectPhosphorusen_US
dc.subjectSeleniumen_US
dc.subjectInorganicen_US
dc.subjectTransition metalsen_US
dc.subjectWoollins' reagenten_US
dc.subjectHeterocyclesen_US
dc.subject.lccQD181.P1G2
dc.subject.lcshPhosphorus compoundsen_US
dc.subject.lcshSelenium compoundsen_US
dc.subject.lcshLigands--Synthesisen_US
dc.titleStudies in phosphorus-selenium chemistryen_US
dc.typeThesisen_US
dc.type.qualificationlevelDoctoralen_US
dc.type.qualificationnamePhD Doctor of Philosophyen_US
dc.publisher.institutionThe University of St Andrewsen_US
dc.publisher.departmentUniversität Leipzigen_US


The following licence files are associated with this item:

    This item appears in the following Collection(s)

    Show simple item record