Lin-Ping Zhang. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2003. / Includes bibliographical references (p. 125-138). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Mode of access: World Wide Web. / Abstracts in English and Chinese.

本研究主要集中在苯胺基配體及全氟苯胺基配體　[N(R')(2,6-R₂C₆H₃)]⁻ [R = Me, Pr{U+2071} ; R' = SiMe₃, SiBu{U+1D57}Me₂, C₆F₅]　衍生出來的一價銅的配位化學，包括其絡合物的合成、結構及氧化反應的研究。 / 第一章概括地介紹了金屬胺他物及銅配合物氧化反應的研究背景。 / 第二章敘述了由苯胺基配體所衍生的一價銅絡合物的裝備及結構。透過苯胺基鹼金屬絡合物 [(M)N(R')(2,6-R₂C₆H₃)] (M = Li, K) 與銅鹵化物CuX (X = Cl, I) 反應，成功合成一系列一價銅絡合物 [Cu₂(L¹)₂(tmeda)] (L¹= [N(SiMe₃)(2,6-Me₂C₆H₃)]⁻)⁻ 及[{Cu(tmeda)₂}{Cu(L{U+207F})₂}] (L{U+207F} = [N(R')(2,6-R₂C₆H₃)]⁻: n = 2, R = Pr{U+2071}, R' = SiMe₃; n = 3, R = Me, R' = SiBu{U+1D57}Me₂; n = 4, R = Pr{U+2071}, R' = SiBu{U+1D57}Me₂; n = 5, R = Me, R' = C₆F₅; n = 6, R = Pri, R' = C₆F₅)。另外，銅碘化物與兩倍的苯胺基鉀絡合物反應[KN(R')(2,6-R₂C₆H₃)] 生成一價銅絡合物 [(tmeda)KCu(L²)₂] (L² = [N(SiMe₃)(2,6-Pr{U+2071} ₂C₆H₃)]) 及 [(tmeda)₂KCu(L⁶)₂] (L⁶ = [N(C₆F₅)(2,6-Pr{U+2071} ₂C₆H₃)]。 / 第三章描述了苯胺基一價銅絡合物跟三苯基膦的氧化反應研究，其中研究不同反應條件，包括反應溫度、氧含量及催化物比例對氧化反應的影響。 / 第四章總結了本研究的成果，同時簡單討論了本課題未來的研究方向。 / The present research work focuses on the synthesis, structure and oxygenation reactivity of a series of copper(I) complexes supported by [N(R')(2,6-R₂C₆H₃)]⁻ (R = Me, Pri ; R' = SiMe₃, SiBu{U+1D57}Me₂, C₆F₅) ligands. / Chapter one gives an overview on the chemistry of metal amides. A brief introduction to copper-dioxygen chemistry is also presented. / Chapter two describes the synthesis and structural characterisation of copper(I) anilides. A series of anilido ligands of the type [N(R')(2,6-R₂C₆H₃)]⁻ (R = Me, Pr{U+2071} ; R' = SiMe₃, SiBu{U+1D57}Me₂, C₆F₅) and tmeda (N,N,N',N'-tetramethylethylenediamine) were employed in our studies. Reactions of CuX (X = Cl, I) with alkali-metal salts of the [N(R')(2,6-R₂C₆H₃)]⁻ ligands yielded the corresponding copper(I) complexes of the type [Cu₂(L¹)₂(tmeda)] (L¹= [N(SiMe₃)(2,6-Me₂C₆H₃)]⁻) or [{Cu(tmeda)₂}{Cu({U+207F})₂}] (L{U+207F} = [N(R')(2,6-R₂C₆H₃)]⁻: n = 2, R = Pr{U+2071}, R' = SiMe₃; n = 3, R = Me, R' = SiBu^(t)Me₂; n = 4, R = Pri, R' = SiBu{U+1D57}Me₂; n = 5, R = Me, R' = C₆F₅; n = 6, R = Pri, R' = C₆F₅). Moreover, reactions of CuI with two equivalents of potassium salts of the [N(R')(2,6-R₂C₆H₃)]⁻ ligands gave copper(I) complexes of the type [(tmeda)KCu(L²)₂] (L₂ = [N(SiMe₃)(2,6-Pr{U+2071} ₂C₆H₃)]) and [(tmeda)₂KCu(L⁶)₂] (L⁶ = [N(C₆F₅)(2,6-Pr{U+2071} ₂C₆H₃)]. / Chapter three deals with the oxygenation reactivity of the copper(I) anilido complexes prepared in this work. The reactions of copper(I) complexes 17-24 with dioxygen led to the conversion of triphenylphosphine to triphenylphosphine oxide. The oxo-transfer reaction was studied under different reaction conditions, such as reaction temperature, oxygen content, and [PPh₃]:[complex] ratio. / Chapter four summarises the results of this research work. An outlook on future directions of this research project is also described in this chapter. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Chen, Yat Kit. / "November 2012." / Thesis (M.Phil.)--Chinese University of Hong Kong, 2013. / Includes bibliographical references. / Abstracts also in Chinese. / Abstract --- p.i / 摘要 --- p.iii / Acknowledgement --- p.iv / Abbreviations --- p.vii / List of Compounds --- p.x / Chapter Chapter 1 - --- An Overview on Late Transition Metal Amides and Copper-Dioxygen Chemistry / Chapter 1.1 --- General Background --- p.1 / Chapter 1.2 --- An Introduction to Late Transition Metal Amides --- p.1 / Chapter 1.3 --- An Introduction to Copper-Dioxygen Chemistry --- p.4 / Chapter 1.4 --- Objectives of This Work --- p.6 / Chapter 1.5 --- References for Chapter 1 --- p.7 / Chapter Chapter 2 - --- Synthetic and Structural Studies of Copper Anilides / Chapter 2.1 --- A General Overview on Anilido Complexes --- p.11 / Chapter 2.2 --- Aims of Our Study --- p.22 / Chapter 2.3 --- Results and Discussion / Chapter 2.3.1 --- Aniline Precursors and Their Alkali Metal Derivatives / Chapter 2.3.1.1 --- Synthesis of Aniline Precursors HL{U+207F} (n = 1-6) --- p.23 / Chapter 2.3.1.2 --- Synthesis of Alkali Metal Derivatives of L{U+207F} (n = 1-6) --- p.25 / Chapter 2.3.1.3 --- Physical Properties of Compounds 7-16 --- p.26 / Chapter 2.3.1.4 --- Molecular Structures of Compounds 7-16 --- p.33 / Chapter 2.3.2 --- Synthesis and Structures of Copper Anilides / Chapter 2.3.2.1 --- Synthesis of Copper(I) Complexes of L{U+207F}(n = 1-6) --- p.62 / Chapter 2.3.2.2 --- Physical Properties of Compounds 17-24 --- p.65 / Chapter 2.3.2.3 --- Molecular Structures of Compounds 17-24 --- p.70 / Chapter 2.3.3 --- Electrochemical Studies --- p.100 / Chapter 2.4 --- Experimentals for Chapter 2 --- p.109 / Chapter 2.5 --- References for Chapter 2 --- p.120 / Chapter Chapter 3 - --- Oxygenation Reactivity Studies / Chapter 3.1 --- A General Review on Oxygenation Copper-Dioxygen Chemistry --- p.128 / Chapter 3.2 --- Aims of Our Study --- p.148 / Chapter 3.3 --- Results and Discussion --- p.149 / Chapter 3.4 --- Experimentals for Chapter 3 --- p.153 / Chapter 3.5 --- References for Chapter 3 --- p.155 / Chapter Chapter 4 - --- Summary and Future Directions --- p.161 / Chapter Appendix A --- General Procedure, Physical Measurements and X-ray Diffraction Analysis --- p.164 / Chapter Appendix B --- NMR Spectra of Compounds --- p.166 / Chapter Appendix C --- Selected Crystallographic Data --- p.191

by Lai Chi Wai. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2001. / Includes bibliographical references (leaves 63-68). / Abstracts in English and Chinese. / Table of Contents --- p.i / Acknowledgments --- p.iii / Abbreviations --- p.iv / Abstract --- p.v / Chapter Chapter 1 --- General introduction / Chapter 1.1 --- Background of phosphines and arsines ligands in metal catalysis --- p.1 / Chapter 1.2 --- Electronic effect of phosphines and arsines ligands in metal catalysis --- p.2 / Chapter 1.3 --- Synthesis of Aryl Phosphines --- p.7 / Chapter 1.4 --- Synthesis of Aryl Arsines --- p.9 / Chapter 1.5 --- The objective of this work --- p.11 / Chapter Chapter 2 --- Palladium catalyzed phosphination of aryl triflates / Chapter 2.1 --- Synthesis of aryl triflates --- p.12 / Chapter 2.2 --- Palladium catalyzed phosphination of aryl triflates --- p.15 / Chapter 2.3 --- Mechanistic studies of phosphination --- p.19 / Chapter Chapter 3 --- Palladium catalyzed arsination of aryl triflates --- p.22 / Chapter 3.1 --- Solvent and catalyst screening in palladium catalyzed arsination --- p.23 / Chapter 3 2 --- Stoichiometry of triphenylarsine --- p.24 / Chapter 3.3 --- Temperature effect of arsination --- p.25 / Chapter 3.4 --- Results of palladium catalyzed arsination --- p.26 / Chapter 3.5 --- Mechanistic studies of arsination --- p.28 / Chapter Chapter 4 --- Green chemistry approach 一 solventless phosphination and arsination / Chapter 4.1 --- Introduction to green chemistry --- p.30 / Chapter 4.2 --- Results of solventless phosphination --- p.31 / Chapter 4.3 --- Results of solventless arsination --- p.33 / Conclusion --- p.36 / Experimental --- p.37 / Reference --- p.63

This thesis involves the design, synthesis and testing of organic hydrophobic ligands. They would act as co-collectors in froth flotation processes to enhance the recovery of sulfidic minerals which have undergone some oxidation on processing and are not efficiently collected by the commercial reagents used in froth flotation. Strong and selective binding to iron(III) oxide/hydroxide surfaces, e.g. goethite, over unwanted silicaceous material was considered essential criteria for such new cocollectors. A general overview of froth flotation processes is given in Chapter 1 as well as a description of the analytical techniques used in this thesis and the features that the ligands must have to act as co-collectors. On the basis of the strong binding to iron(III) surfaces of the organic ligand Irgacor 419®, used commercially as a corrosion inhibitor for iron, this compound was studied as a potential co-collector. Adsorption isotherms were determined by UV-Vis spectroscopy for two carboxylic acids that may also bind strongly to goethite, the results of which are discussed in Chapter 2. Chapter 3 involves the measurement of the strength of binding of one the most widely used type of collectors for sulfide ores, potassium ethyl xanthate. Complications in the analysis of materials in solution by both ICP-OES and UV-Vis spectroscopy arose due to the instability of potassium ethyl xanthate in solution, making determination and interpretation of isotherms difficult. The determination of adsorption isotherms for 2-mercaptobenzothiazole, which showed weak binding to goethite as well as to silica, and the mode of binding of 2-mercaptobenzothiazole on copper(I) surfaces is reported in Chapter 4. A crystal structure was obtained in which four units of 2-mercaptobenzothiazole bridge two nickel atoms through the nitrogen atom and the exocyclic sulfur and is considered as a model for binding to sulfidic minerals. Chapter 5 looks at the strength of binding to goethite and silica of various hydroxamic acids. Benzohydroxamic acid was initially selected for study since hydroxamates are known to act as collectors for oxidized materials. Unpredictably, benzohydroxamic acid showed strong binding to a goethite surface and did not release any iron from the surface into solution, which would have been predicted due to its known strong chelating abilities to iron(III). The X-ray structure determination of the first example of a dinuclear Fe(III) hydroxamate complex showed this to have -oxo bridge formed by the hydroxamate unit and supports multisite attachment between this ligand and the surface, as suggested by adsoption isotherms. Simple models based on this dinucleating motif provide plausible modes of multisite attachment to a goethite surface. Competitive binding studies provided a way of ranking the ability to bind to goethite of acetohydroxamic acid, which was not suitable for analyses by either ICP-OES or UV-Vis spectroscopy. Of the ligands studied in this chapter acetohydroxamic acid was found to bind most strongly to goethite followed by benzohydroxamic acid. In Chapter 6, the attachment to goethite and silica of a series of phosphonic acids is investigated. All show a very high binding strength to goethite. Froth flotation experiments at a laboratory scale are described in Chapter 7. The types of ligand that showed strong binding to goethite in adsorption isotherms experiments were tested as co-collectors in different ores and conditions. There is not a simple correlation between adsorption isotherm data and flotation performance as co-collectors because other factors, besides strength of binding, affect the system. Benzohydroxamic acid was the ligand that increased the grade/recovery of the process in all the cases studied. Irgacor 419® enhances the grade/recovery curve for Palabora ore and phenyl malonic acid for Kennecott ore. These results support the original proposition that it may be possible to increase the recovery of oxidized particles substantially by using a blend of collectors which includes a compound to target the oxidized sites.

>Magister Scientiae - MSc / This thesis reports on the syntheses of complexes of (arene) ruthenium (II) isoniazid Schiff base ligands for antimicrobial studies. Isoniazid Schiff base ligands; isonicotinyl acid (2-hydroxy-5- methyl-benzilidene)-hydrazide (L1), isonicotinyl acid (2-hydroxy-5-methoxy-benzilidene)- hydrazide (L2), isonicotinyl acid (-5-chloro-2-hydroxy-benzilidene)-hydrazide (L3), isonicotinyl acid (-5-bromo-2-hydroxy-benzilidene)-hydrazide (L4), isonicotinyl acid (2-hydroxy-5-nitrobenzilidene)- hydrazide (L5) were prepared by condensation reaction under reflux from equimolar amounts of isioniazid, which is an amine, with five different aldehyde moieties. Ruthenium (II) complexes of these isoniazid Schiff base ligands (C1 - C5) were prepared in an ethanolic solution under reflux and inert atmosphere at 60°C using Schlenk techniques. Fourier transform infrared spectroscopy (FTIR), ultraviolet – visible spectroscopy, thermogravimetric analysis, nuclear magnetic resonance and elemental analysis were the characterization techniques that confirmed the successful preparation of the ligands. All the ligands spectra displayed the imine functional group peak which confirmed the successful preparation. The ligands L1 – L5 and the complexes C1 – C5 were subjected to similar characterization techniques which further confirmed the successful syntheses and the coordination of metal and ligand by displaying a shift in their respective imine peaks and transitions values. All the synthesized compounds were subjected to a standard antimicrobial test using three microorganisms, Staphylococcus aureus, Methicillin resistant Staphylococcus aureus and Pseudomonas aeruginosa. Out the ten compounds tested, only ligand L5 gave the best results against Staphylococcus aureus.

Wan, Chi Ling. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2009. / Includes bibliographical references. / Abstracts in English and Chinese. / Table of Contents --- p.vi / Acknowledgement --- p.i / Abstract --- p.ii / 摘要 --- p.iv / List of Compounds Synthesized in This Work --- p.x / Abbreviation --- p.xi / Chapter Chapter 1 --- Synthesis of Group 1 and 2 Metal Bis(thiophosphinoyl) Complexes / Chapter 1.1 --- Introduction --- p.1 / Chapter 1.1.1 --- General Aspects of Thiophosphinoyl Ligands --- p.1 / Chapter 1.1.2 --- General Aspects of Group 1 and 2 Thiophosphinoyl Metal Complexes --- p.6 / Chapter 1.1.3 --- Objectives of This Work --- p.10 / Chapter 1.2 --- Results and Discussion --- p.11 / Chapter 1.2.1.1 --- Synthesis of Monoanionic Bis(thiophosphinoyl) Lithium Complex --- p.11 / Chapter 1.2.1.2 --- Spectroscopic Properties of 42 --- p.11 / Chapter 1.2.1.3 --- Molecular Structure of [Li{(S=PPh2)CH}(THF)(Et20)] (42) --- p.12 / Chapter 1.2.2.1 --- Synthesis of Dianionic Bis(thiophosphinoyl) Magnesium Complex --- p.14 / Chapter 1.2.2.2 --- Spectroscopic Properties of 43 --- p.14 / Chapter 1.2.2.3 --- Molecular Structure of [MgC(PPh2=S)(THF)]2.2THF (43) --- p.15 / Chapter 1.3 --- Experimental for Chapter 1 --- p.17 / Chapter 1.4 --- References for Chapter 1 --- p.19 / Chapter Chapter 2 --- Synthesis and Reactivity of Group 14 Metal Bis(thiophosphinoyl) Complexes / Chapter 2.1 --- Introduction --- p.24 / Chapter 2.1.1 --- General Aspects of Low Valent Group 14 Organometallic Compounds --- p.24 / Chapter 2.2 --- Results and Discussion --- p.32 / Chapter 2.2.1.1 --- "Synthesis of 1,3-Distannacyclobutane and 1,3-Diplumbacyclobutane" --- p.32 / Chapter 2.2.1.2 --- Spectroscopic Properties of 74 and 75 --- p.33 / Chapter 2.2.1.3 --- Molecular Structures of [Sn{u2-C(Ph2P=S)2}]2.THF (74) and [Pb{u2-C(Ph2P=S)2}]2.THF(75) --- p.34 / Chapter 2.2.2.1 --- "Reaction of 1,3-Diplumbacyclobutane with Chalcogens" --- p.38 / Chapter 2.2.2.2 --- Spectroscopic Properties of 78 and 79 --- p.39 / Chapter 2.2.2.3 --- "Molecular Structures of [PbE{C(PPh2=S)2}] (E = S (78),Se (79))" --- p.39 / Chapter 2.2.3.1 --- Synthesis of Chlorogermylene and Chlorostannylene --- p.44 / Chapter 2.2.3.2 --- Spectroscopic Properties of 80 and 81 --- p.44 / Chapter 2.2.3.3 --- "Molecular Structures of [MCl{CH(PPh2=S)2}] (M = Ge (80),Sn (81))" --- p.45 / Chapter 2.2.4.1 --- Reaction of Chlorogermylene with Chalcogens --- p.49 / Chapter 2.2.4.2 --- Spectroscopic Properties of 82 --- p.50 / Chapter 2.2.4.3 --- Molecular Structure of [GeCl{CH(PPh2=S)2}(u-S)]2.4THF (82) --- p.51 / Chapter 2.2.4.4 --- Reaction of Chlorostannylene with Pb{N(SiMe3)2}2 --- p.53 / Chapter 2.3 --- Experimental for Chapter 2 --- p.54 / Chapter 2.4 --- References for Chapter 2 --- p.60 / Chapter Chapter 3 --- Synthesis of Group 13 Metal Bis(thiophosphinoyl) Complexes / Chapter 3.1 --- Introduction --- p.65 / Chapter 3.1.1 --- General Aspects of Group 13 Organometallic Chemistry --- p.65 / Chapter 3.1.2 --- General Aspects of Group 13 Metal Complexes Bearing Phosphoranoimine or Phosphoranosulfide Ligands --- p.67 / Chapter 3.2 --- Results and Discussions --- p.72 / Chapter 3.2.1 --- Synthesis of Group 13 Metal Bis(thiophosphinoyl) Complexes --- p.72 / Chapter 3.2.2 --- Spectroscopic Properties of 108-110 --- p.72 / Chapter 3.2.3 --- "Molecular Structures of [MCl{C(PPh2=S)2}]2 (M = A1 (108),Ga (109), In (110))" --- p.73 / Chapter 3.3 --- Experimental for Chapter 3 --- p.79 / Chapter 3.4 --- References for Chapter 3 --- p.82 / Chapter Chapter 4 --- Synthesis of Group 4 Metal Bis(thiophosphinoyl) Complexes / Chapter 4.1 --- Introduction --- p.86 / Chapter 4.1.1 --- General Aspects of Group 4 Early Transition Metal Complexes --- p.86 / Chapter 4.2 --- Results and Discussion --- p.92 / Chapter 4.2.1 --- Synthesis of Group 4 Metal Bis(thiophosphinoyl) Complexes --- p.92 / Chapter 4.2.2 --- Spectroscopic Properties of 125-128 --- p.93 / Chapter 4.2.3 --- Molecular Structures of [Hf(NMe2)3{CH(PPh2=S)2}] (126) --- p.94 / Chapter 4.3 --- Experimental for Chapter 4 --- p.97 / Chapter 4.4 --- References for Chapter 4 --- p.100 / Appendix I / Chapter A. --- General Procedures --- p.104 / Chapter B. --- Physical and Analytical Measurements --- p.104 / Chapter C. --- X-ray Crystallographic Determination --- p.105 / Appendix II / "Table A.1. Selected Crystallographic Data for Compounds 42,43,74 and 75" --- p.108 / Table A.2. Selected Crystallographic Data for Compounds 77-80 --- p.109 / "Table A.3. Selected Crystallographic Data for Compounds 81,108-110 and 126" --- p.110 / Appendix III / Chapter A. --- Future Work --- p.111

Lai, Yin Man. / Thesis submitted in: November 2008. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2009. / Includes bibliographical references. / Abstracts in English and Chinese. / ACKNOWLEDGEMENT --- p.I / ABSTRACT --- p.II / 摘要 --- p.IV / ABBREVIATIONS --- p.V / LIST OF COMPOUNDS --- p.VI / TABLE OF CONTENTS --- p.IX / Chapter CHAPTER 1 --- A 2-PYRIDYL AMIDO LIGAND CONTAINING A PENTAFLUOROPHENYL SUBSTITUENT --- p.1 / Chapter 1. l --- General Background --- p.1 / Chapter 1.2 --- Examples of Amido Ligands --- p.3 / Chapter 1.3 --- An overview on Amido Ligands Containing Electron-withdrawing Substituents --- p.5 / Chapter 1.4 --- Objectives of This Work --- p.7 / Chapter 1.5 --- Results and Discussion --- p.8 / Chapter 1.5.1 --- Preparation of HLC6F5 (1) and its Potassium Derivatives --- p.8 / Chapter 1.5.2 --- Physical Characterization of Compounds 1-3 --- p.10 / Chapter 1.5.3 --- Molecular Structures of Compounds 2 and 3 --- p.13 / Chapter 1.6 --- Experimentals for Chapter 1 --- p.19 / Chapter 1.7 --- References for Chapter 1 --- p.22 / Chapter CHAPTER 2 --- "ZIRCONIUM(IV), VANADIUM(III) AND CHROMIUM(III) COMPLEXES DERIVED FROM THE [N(C6F5)(2-CsH3N-6-ME)] LIGAND" --- p.27 / Chapter 2.1 --- "An Overview on Zr(IV), V(III) and Cr(III) Complexes Supported by 2-Pyridyl Amido Ligands" --- p.27 / Chapter 2.2 --- Recent Results from our Group --- p.32 / Chapter 2.3 --- Objectives of this work --- p.33 / Chapter 2.4 --- "Synthesis and Structures of Tris(amido) Complexes of Zr(IV), V(III) and CR(III)" --- p.34 / Chapter 2.4.1 --- "Synthesis of [Zr(LC6F5)3(Cl) ´Ø C7H8] (4), V(LC6F5)3 (5) and [Cr(LC6F5)3] (6)" --- p.34 / Chapter 2.4.2 --- Molecular Structures of [Zr(LC6F5)3(Cl)´ØC7H8] (4)f and [Cr(LC6F5)3] (6) --- p.37 / Chapter 2.5 --- Experimentals for Chapter 2 --- p.43 / Chapter 2.6 --- References for Chapter 2 --- p.45 / Chapter CHAPTER 3 --- "MANGANESE(II), IRON(II), COBALT(II) AND NICKEL(II) COMPLEXES OF THE [N(C6F5)(2-C5H3N-6-ME)] LIGAND" --- p.49 / Chapter 3.1 --- A Brief Review on Amides of the Late Transition Metals --- p.49 / Chapter 3.2 --- Examples of Late Transition Metal Complexes Supported by 2-Pyridyl Amido Ligands --- p.51 / Chapter 3.3 --- Objectives of our studies --- p.53 / Chapter 3.4 --- "Synthesis and Structures of Bis(amido) Complexes of Mn(II), Fe(II), Co(II) and NI(II)" --- p.54 / Chapter 3.4.1 --- "Synthesis of [M(LC6F5)2(tmeda)] (M = Mn (7), Fe (8), Co (9), Ni (10)]" --- p.54 / Chapter 3.4.2 --- Molecular Structures of Complexes 7-10 --- p.57 / Chapter 3.5 --- "Synthesis, Structure and Reactivity of a Mono(amido) Fe(II) Complex" --- p.61 / Chapter 3.5.1 --- Synthesis of [Fe(LC6F5)(CI)(tmeda)](11) --- p.61 / Chapter 3.5.2 --- Physical Characterization of Compound 11 --- p.62 / Chapter 3.5.3 --- Molecular Structures of Compound 11 --- p.62 / Chapter 3.5.4 --- Reactivity Studies of [Fe(LC6F5)(Cl)(tmeda)] (11) --- p.66 / Chapter 3.6 --- Synthesis of Fe(III) Tri(amido) Complex --- p.69 / Chapter 3.7 --- Experimentals for Chapter 3 --- p.70 / Chapter 3.8 --- References for Chapter 3 --- p.73 / Chapter CHAPTER 4 --- SUMMARY OF THE PRESENT RESEARCH WORK --- p.75 / TABLE OF APPENDIX --- p.79 / "General Procedures, Physical Measurements and X-Ray Structural Analysis" --- p.80 / 1HNMR of HCC6F5(1) --- p.82 / 13CNMR of HLC6F5(1) --- p.83 / 19FNMR of HLC6F5(1) --- p.84 / 1HNMR of [K(LC6F5)(tmeda)]2 (2) --- p.85 / 13CNMR OF [K(LC6F5)(tmeda)]2 (2)) --- p.86 / 19FNMR of [K(LC6F5)(TMEDA)]2 (2)) --- p.87 / 1HNMR of [K(LC6F5)(thf)2]2 (3) --- p.88 / 13CNMR of [K(LC6F5)(thf)2]2 (3) --- p.89 / 19FNMR OF [K(LC6F5)(THF)2]2 (3) --- p.90 / 1HNMR of Zr(LC6F5)3(Cl).(C7H8)] (4) --- p.91 / Selected crystallographic data of complexes 2 and 3 --- p.94 / Selected crystallographic data of complexes 4 and 6 --- p.95 / Selected crystallographic data of complexes 7 and 8 --- p.96 / Selected crystallographic data of complexes 9 and 10 --- p.97 / Selected crystallographic data of complex 11 --- p.98

Key understanding of potential transformations that may occur on silver nanoparticle (AgNP) surface upon interaction with naturally ubiquitous organic ligands (e.g., −SH (thoil), humic acid, or −COO (carboxylate)) is limited. Herein we investigated how dissolved organic carbon (DOC), −SH (in cysteine, a well-known Ag+ chelating agent), and −COO (in trolox, a well-known antioxidant) could alter the colloidal stability, dissolution rate, and toxicity of citrate-functionalized AgNPs (citrate–AgNPs) against a keystone crustacean Daphnia magna. Cysteine, DOC, or trolox amendment of citrate–AgNPs differentially modified particle size, surface properties (charge, plasmonic spectra), and ion release dynamics, thereby attenuating (with cysteine or trolox) or promoting (with DOC) AgNP toxicity. Except with DOC amendment, the combined toxicity of AgNPs and released Ag under cysteine or trolox amendment was lower than of AgNO3 alone. The results of this study show that citrate–AgNP toxicity can be associated with oxidative stress, ion release, and the organism biology. Our evidence suggests that specific organic ligands available in the receiving waters can differentially surface modify AgNPs and alter their environmental persistence (changing dissolution dynamics) and subsequently the toxicity; hence, we caveat to generalize that surface modified nanoparticles upon environmental release may not be toxic to receptor organisms.

Abstract not available

This work investigated the use of large tetradentate mixed nitrogen and oxygen donor macrocycles as potential ligands for titanium(IV).These large ligands are capable of encapsulating the metal ion, thereby protecting it from reacting further. In addition, titanium complexes of this type had not been reported previously.Molecular modelling was utilised to evaluate and predict the coordinating potential of the macrocycles investigated.An alternative synthetic strategy was needed to achieve coordination complexes with titanium. This involved the use of a benzene based solvent system and rigorously dry reaction conditions.The final part of the work involved a detailed study of the kinetics of the hydrolysis of the titanium complexes investigated. / Doctor of Philosophy (PhD)