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Lanthanide compounds, specifically those containing europium and terbium can exhibit luminescent properties when combined with ligands that promote this characteristic. Lanthanide luminescence has proven to have an array of useful applications, one of which is the formation of luminescent powders for exposure of latent fingerprints. The aim of this study was to synthesise a novel ligand to support luminescent character in europium and terbium compounds, and then dope these compounds in to talcum powder. This resulting powder would ideally give exposure of latent fingerprints that can then be enhanced, through excitation of the luminescent compounds dispersed in the powder. A novel (Me)₃CN(CH₂P(O)Ph₂)₂ ligand (p=o) was synthesised, and in turn was used to synthesis a range of Ln(β‐diketonate)₃(p=o) compounds. These compounds were assess...
The reaction of C,N-coordinated gold(III) dihalides; BpAuCl₂ (Bp = 2 benzylpyridyl), AnpAuCl₂ (Anp = 2 anilinopyridyl) and TypAuCl₂ (Typ = 2 tolylpyridyl) with catecholate ligands in hot methanol and trimethylamine produced metallacycles with structural isomers of the general formula (C,N)Au{O,O}. Similarly, BpAuCl₂ and AnpAuCl₂ were reacted with thiourea ligands to form complexes giving high yield and good purity with the general formula (C,N)Au{PhNCSNR₂}+, by means of the addition of BPh₄- for precipitation. X-ray crystal structures of the compounds [AnpAu{PhNCSNMe₂}]BPh₄ and [AnpAu{PhNCSNCy₂}]BPh₄ confirmed the coordination of the thiourea to the gold centre through the N and S atoms. In both cases the geometry around the gold atom is square-planar with complex [AnpAu{PhNCSNCy₂}]BPh₄ showing a slightly more puckered conformation tha...
This thesis presents the studies on the multifunctional alkylation of the metalloligand [Pt₂ (μ-S)₂(PPh₃)₄] 1.1. Multifunctional organic groups which include semicarbazone and thiosemicarbazone, urea, isocyanate, guanidine, ketones and amides react with 1.1 to generate the corresponding functionalised derivatives containing thiolate ligands produced by alkylation of one or both sulfide centres. Polymers with suitable electrophilic branches also react to immobilise 1.1. By using Electrospray Ionisation Mass Spectrometry (ESI-MS) as the monitoring technique, [Pt₂ (μ-S)₂(PPh₃)₄] was employed as a productive template for structurally and chemically diverse thiolate-platinum complexes. Before this study, 1.1 was known to be one of the best building blocks for multimetallic molecules through the exceptional ligating ability of the two sulfid...
The reaction of N,O-donor ligands hippuric acid and N-phenylanthranilic acid with [PtCl???(COD)] (COD = 1,5-cyclooctadiene) in dichloromethane and in the presence of silver(I) oxide yields the complexes [Pt{OC(O)CH???N(COPh)}(COD)] and [Pt{OC(O)(C???H???)N(Ph)}(COD)]. Several ligand-substitution reactions were performed using complex [Pt{OC(O)CH???N(COPh)}(COD)] and a variety of phosphines, to produce [Pt{OC(O)CH???N(COPh)}(PPh???)???].1.5.CH???Cl???, [Pt{OC(O)CH???N(COPh)}(dppe)][dppe = 1,2-bis(diphenylphosphino)ethane], [Pt{OC(O)CH???N(COPh)}(PTA)???] (PTA = 1,3,5-triaza-7-phosphaadamantane) and [Pt{OC(O)CH???N(COPh)}(dppf)] [1,1???-bis(diphenylphosphino)ferrocene]. The X-ray crystal structure of [Pt{OC(O)CH???N(COPh)}(COD)] was obtained which showed the hippurate ligand coordinated to platinum via the nitrogen and oxygen atoms. Atte...
This thesis reports the synthesis and characterisation of eight new platinum thiourea complexes. Thiourea dianion complexes of the type (Ph???P)???PtSC(=NR)NPh, R=Me, Et, Pr???, Pr???, Bu??? and (Ph???P)???PtSC(=NPh)NR R=Bu?? , p-tol, and the thiourea monoanion complex of the type [(Ph???P)???PtSC(=NEtH)NPh]??? were synthesised. This research confirms the prediction made by Henderson et al that asymmetrically substituted thiourea dianion complexes could form isomers. NMR studies show that the kinetically favoured isomer is formed initially, and then undergoes a solution phase isomerisation process to form the thermodynamically favoured isomer. Evidence that this isomerisation is affected by difference in substituent size and the energy difference between the two structures was obtained both experimentally, by use of NMR spectroscopy te...
John Ruskin (1819-1900) is most immediately known today as a very influential art critic, scholar, and professor. However, among his many interests also figures a deep apprehension regarding the socio-economic conditions of his country in a time marked by the profound and rapid transformations associated with the rise of industrial capitalism. Since Ruskin sensed that the core elements of these transformations were inspired and/or legitimised by the emergent ‘classical political economy’, he felt compelled to undertake a critique of it, and to advance an alternative, or ‘true’, political economy. The main objective of this dissertation is to provide a systematised reading of Ruskin’s economic writings, and show that they possess relevant economic content. This is compounded by a concern to see Ruskin’s standpoint as an instance of what...
This thesis describes the incorporation of carbohydrate groups in thiourea, 1, or iminophosphorane, 2, ligands. Several carbohydrate acyl thioureas, 3, were synthesised from the reaction of protected and unprotected D‐glucosamine with acyl isothiocyanates, RCONCS. Internal hydrogen‐bonding forms a planar six‐membered ring, which locks the thiourea into an Z,E,Z‐anti conformation as shown by 1H NMR spectroscopy and confirmed by X‐ray structure determination of two examples. As neutral ligands to Rh(III), Rh(I), Ru(II), Pd(II), Pt(II) and Au(I) they bond through the sulfur atom with retention of the six‐membered ring and the Z,E,Z‐anti conformation. This was confirmed by two X‐ray structure determinations on Rh(III) and Pd(II) examples which also showed the new hydrogen‐bond formed by HN2 to a halide on the metal. Deprotonation of the l...
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