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dc.contributor.advisorHenderson, William
dc.contributor.authorSutton, Ryan
dc.date.accessioned2019-04-08T01:58:24Z
dc.date.available2019-04-08T01:58:24Z
dc.date.issued2019
dc.identifier.citationSutton, R. (2019). The synthesis of water-soluble analogues of Pt₂(μ₂-S)₂(PPh₃)₄ (Thesis, Master of Science (Research) (MSc(Research))). The University of Waikato, Hamilton, New Zealand. Retrieved from https://hdl.handle.net/10289/12443en
dc.identifier.urihttps://hdl.handle.net/10289/12443
dc.description.abstractPlatinum has a very rich chemistry with sulfur, and this field has been extensively studied. Of particular interest are complexes containing the {Pt₂(μ₂-S)₂} core, comprising two platinum atoms with μ₂-sulfurs bridging through a flexible hinge. These complexes can act as potent metalloligands (through the two sulfurs) toward a wide range of transition metal and other centres, allowing for the synthesis of complexes with trinuclear mixed-metal cores {Pt₂(μ₃-S)₂M} (M = heterometal). The {Pt₂(μ₂-S)₂} core is also highly nucleophilic and alkylated by the mildest of reagents. The ancillary ligands coordinated to the {Pt₂(μ₂-S)₂} core are primarily triphenylphosphine (PPh₃), resulting in the complexes being significantly insoluble in water, preventing any forms of bioactivity or biphasic catalysis from being assessed. This research project has widened the scope of {Pt₂(μ₂-S)₂} complexes via the synthesis of the new water-soluble complexes {Pt₂(μ₂-S)₂}(PTA)₄, [Pt₂(μ₃- S)₂(PTA)₄Rh(cod)]Cl, and [Pt₃(μ3-S)₂(PTA)6]²⁺ (PTA = 1,3,5-triaza-7- phosphaadamantane, cod = 1,5-cyclooctadiene) that were characterised by electrospray ionisation mass spectrometry (ESI-MS) and phosphorus-31 nuclear magnetic resonance spectroscopy (³¹P{¹H} NMR). The complex [Pt₃(μ₃- S)₂(PTA)₆]²⁺ was synthesised during the research into the use of a sulfide exchange column as an alternative source of sulfide for the synthesis of Pt₂(μ₂- S)₂(PTA)₄. The water-soluble phosphine ligands tris(2-carboxyethyl)phosphine (TCEP) and monosulfonated triphenylphosphine [TPPMS]⁻ were determined to be unsuitable ligands for complexes of the general form {Pt₂(μ₂-S)₂}(L)₄ (L = TCEP, [TPPMS]⁻). During these attempted syntheses the complex {Pt₂(μ₂-S)₂} (cod)₂ was successfully produced and characterised with ESI-MS, ¹H NMR, ¹H-¹H COSY, and ¹³C-¹H HSQC (Proton nuclear magnetic resonance spectroscopy, Correlation Spectroscopy, Heteronuclear Single Quantum Coherence). The use of thioacetamide (CH₂C(S)NH₂) as an alternative source of sulfide in the synthesis of {Pt₂(μ₂-S)₂}(PPh₃)₄ was found to be a poor substitute for the well established Na₂S·9H₂O. The reaction does result in [Pt(CH₃C(S)NH)(PPh₃)₂]⁺+, subsequently isolated as the BPh₄- salt, [Pt(CH₃C(S)NH)(PPh₃)₂](BPh₄) and was characterised by ESI-MS and ³¹P{1H} NMR. The X-ray crystal structure of the by-product trans-Pt(SC(O)CH₃)₂(PPh₃)₂ was obtained.
dc.format.mimetypeapplication/pdf
dc.language.isoen
dc.publisherThe University of Waikato
dc.rightsAll items in Research Commons are provided for private study and research purposes and are protected by copyright with all rights reserved unless otherwise indicated.
dc.subjectChemistry
dc.subjectPlatinum
dc.subjectPt2S2
dc.titleThe synthesis of water-soluble analogues of Pt₂(μ₂-S)₂(PPh₃)₄
dc.typeThesis
thesis.degree.grantorThe University of Waikato
thesis.degree.levelMasters
thesis.degree.nameMaster of Science (Research) (MSc(Research))
dc.date.updated2019-04-07T23:15:35Z
pubs.place-of-publicationHamilton, New Zealanden_NZ


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