Chapter 1 reviews the coordination behaviour of the 6-diphenylphosphino-2,2'-bipyridine, 6-anilino-2,2'-bipyridine, 2,2'-bipyridyl-6-one, 6-N-methylanilino-2,2'-bipyridine, 6-piperidyl-2,2'-bipyridine and 2-(phenylamino)-1,10-phenanthroline ligands. These ligands are all tridentate and contain well established chelating fragments viz., 2,2'-bipyridine and 1,10-phenanthroline. Thus the review of their coordination provides insight into the expected coordination of the 2-diphenylphosphino-1,10-phenanthroline (Ph2Pphen) ligand. The synthesis and characterisation of this ligand is described in Chapter 2. Chapter 3 describes the synthesis and characterisation of a range of Ph2Pphen ligand-bridged dicopper(l) complexes. It has been shown that Ph2Pphen reacts with a suitable copper(l) precursor, [Cu(MeCN)4]+, to form the versatile dinuclear [Cu2(u-Ph2Pphen)2(MeCN)2]2+complex cation containing two bridging Ph2Pphen ligands; the structure of the SbF6 salt of this complex has been determined X-ray crystallographically. This complex possesses labile acetonitrile ligands which have been substituted by a variety of neutral and anionic ligands. Complexes prepared this way include [Cu2(u-Ph2Pphen)2(u-CI)]+, [Cu2(u-Ph2Pphen)2(u-I)]+, [Cu2(u-Ph2Pphen)2(py)2]2 +, [Cu2(u-Ph2Pphen)2{u-S2CN(Et)2}]+, [Cu2(u-Ph2Pphen)2(n-bipy)]2+ and [Cu2(u-Ph2Pphen)2(n-phen)]2+. X-ray structure determinations have been completed for [Cu2(u-Ph2Pphen)2{u-S2CN(Et)2}]+ and [Cu2(u-Ph2Pphen)2(n-bipy)]2+. The X-ray crystal structures of these ligand-bridged complexes confirm that the phosphorus atom coordinates to one copper atom while the phenanthroline fragment chelates to the other copper atom with the result that each metal atom has a tetrahedral geometry. Chapter 4 reviews the synthesis and characterisation of palladium and platinum complexes of the 2-diphenylphosphino-1, 10-phenanthroline (Ph2Pphen) ligand. The comproportionation reaction with Pd(II) and Pd(0) afforded the dinuclear complex [Pd2(u-Ph2Pphen)2](BF4)2. The reaction of Ph2Pphen with platinum resulted in ill-defined products that could not be isolated and characterised. / Thesis (M.Sc.)-University of Natal, Pietermaritzburg, 1998

Transition metal complexes derived from Schiff bases have rendered an important contribution to the development of modern coordination chemistry. Various stable compounds have been prepared having synthetic, biological, and physicochemical interest. In particular, complexes of salicylaldimines, B-ketoamines, and closely related ligand systems have been investigated.

Calixarenes are a class of macrocyclic compounds that have garnered interest in large part because of their ability to form host-guest complexes with various types of molecules. For all of the studies of complex formation by calixarenes, most of the work to date has concentrated upon the smaller calixarenes, and little is understood about the relationship between the complexes formed when in solution and that observed in the solid state. The first part of the study, presented in Chapter 3, is of the solid-state properties of two of the larger calixarenes, and in comparison to other reported structures reveals patterns to the observed conformations both in the solid state and in solution. The formation of metal complexes has also been investigated and has focused extensively upon the metals as guests. Thus, the ability of the calixarenes to act as ligands in inorganic complexes has been virtually untapped, despite the polyoxo binding site they can easily provide, and very few metallocalixarenes have been reported. The second part of this study goes beyond the simple solid-state properties of such compounds, and involves the synthesis of several metallocalixarenes as part of a project directed at the functionalization of calixarenes with the components of a class of catalysts known to polymerize various olefins. These catalysts, commonly referred to as Ziegler-Natta catalysts, are introduced in Chapter 4. The new compounds presented here--three new aluminocalixarenes in Chapter 5 and a new titanocalixarene in Chapter 6--were synthesized so as to contain some of the same components observed in several of the other catalysts. These new compounds have been characterized crystallographically as well as through proton and multinuclear NMR, and observed conformational patterns are discussed.

This Thesis describes the synthesis and characterisation of a series ofbisphenolate supported samarium borohydride, amide and zwitterionic rare earth complexes and their ability to effect the ring opening polymerisation (ROP) of cyclic esters and methylmethacrylate (MMA). Chapter 1 introduces ROP from both an industrial and an academic perspective and describes in detail the research in this area, with emphasis on rare earth initiators. The lanthanide elements and the bisphenolate ligand are also introduced. Chapter 2 describes the synthesis and characterisation ofbisphenolate supported samarium borohydride and silylamide complexes. Chapter 3 describes the ability of a selection of samarium borohydride and amide complexes to effect the ROP of the cyclic esters s-caprolactone (f-CL) and rac- lactide (rac-LA). Emphasis is placed on the effect that the nature of the bisphenolate pendant arm and the initiating moiety has on the polymerisation process. Chapter 4 describes the synthesis and characterisation of rare earth zwitterionic complexes and the ability ofa range of these complexes to effect the ROP of s-Cl. and rac-lactide. Mechanistic aspects ofthe ROP process will be discussed, as will the ability of these complexes to yield amide functionalised poly(rac-LA). Chapter 5 describes the ability ofbisphenolate samarium borohydride complexes to initiate the polymerisation of MMA. The experimental work conducted as part of this study is further supported computationally by calculations at the DFT level, both aspects will be described. Aspects concerning the synthesis and characterisation of the related borohydride derivative [Sm(N2siMe3NNPY)(BH4)2Li]oo will also be emphasised. Chapter 6 contains full experimental and characterising data for all 0 f the new compounds reported in this Thesis. Appendices A- T contain tables of selected crystallographic data for all new crystallographically characterised complexes described in this Thesis (partially on CD).

Ku, Ka Wai. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2011. / Includes bibliographical references. / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstract also in Chinese.

by Weng Linhong. / Thesis (Ph.D.)--Chinese University of Hong Kong, 1995. / Includes bibliographical references (leaf 162). / ACKNOWLEDGMENTS --- p.i / ABSTRACT --- p.ii / ABBREVIATIONS --- p.iv / LEGEND OF COMPOUNDS --- p.v / Chapter CHAPTER1 --- METALLATION OF α-SUBSTITUTED PICOLINE DERIVATIVES --- p.1 / Chapter 1.1 --- Introduction --- p.1 / Chapter 1.1.1 --- Overview of Lithiation of Alkyl --- p.1 / Chapter 1.1.2 --- General Review of N-functionalized Alkyl Ligand --- p.3 / Chapter 1.1.3 --- The Substituted Methylpyridine Ligands and Their Derivatives --- p.6 / Chapter 1. --- Properties of Some α-Substituted Methylpyridine Ligand --- p.6 / Chapter 2. --- Electronic Properties of Substituted Methylpyridyl Ligand --- p.7 / Chapter 3. --- Some Structure of the Metal Derivatives of the N-Functionalised Alkyl Ligand --- p.8 / Chapter 4. --- Coordination Behavior of the Alkyl Ligand --- p.12 / Chapter 1.2 --- Results and Discussion --- p.14 / Chapter 1.2.1 --- Syntheses of N-Functionalised Lithium Alkyl Complexes --- p.14 / Chapter 1. --- "Synthesis of (tert-Butyldimethylsilyl)methylpyridine, CH2(SiButMe2)C5H4N-2 33 (picß H)" --- p.14 / Chapter 2. --- Lithiation of [CH(SiButMe2)C5H4N-2]´ؤPreparation of Compound 34 --- p.15 / Chapter 3. --- The Alkylation of [Li{CH(SiButMe2)C5H4N-2}(tmeda)]2 34 --- p.15 / Chapter 4. --- Metallation of Benzylpyridine CH2(Ph)C5H4N-2 (picφH)´ؤPreparation of Compound 36 --- p.17 / Chapter 5. --- Preparation of Compounds CHPh(SiMe3)C5H4N-2 37 (picφ'H) and its Lithium Compound [{CPh(SiMe3)C5H4N-2}Li(tmeda)] 38 --- p.17 / Chapter 6. --- The Lithiation of CH2(SiButMe2)C5H4N-2 33 and CHPh(SiMe3)C5H4N-2 37 in the absence of tmeda --- p.18 / Chapter 1.2.2 --- Characterization of the Ligands and Their Lithium Derivatives --- p.19 / Chapter 1. --- NMR characterization of ligand CH2(SiButMe2)C5H4N-2 33 --- p.19 / Chapter 2. --- NMR characterization of [Li{CH2(SiButMe2)C5H4N-2}(tmeda)]2 34 --- p.20 / Chapter 3. --- NMR of CH(Me)(SiButMe2)C5H4N-2 35 --- p.29 / Chapter 4. --- 1H and 13C NMR of CH(Ph)(SiMe3)C5H4N-2 37 --- p.29 / Chapter 5. --- 1H and 13C NR spectra of Ligand [ {CPh(SiMe3)C5H4N-2} (tmeda)] 38 --- p.30 / Chapter 6. --- NMR characterization of [{CH(SiButMe2)C5H4N-2}Li(Et20)]2 39 --- p.37 / Chapter 7. --- The 7Li NMR of the Lithium N-functionalized Alkyl compounds --- p.37 / Chapter 8. --- Mass spectroscopy of some picoline derivatives --- p.38 / Chapter 1.2.3 --- "The X-Ray Structures of Lithium Complexes 34, 36, 38 and 39" --- p.39 / Chapter 1. --- The structure of [Li{CH(SiButMe2)C5H4N-2}(tmeda)]2 34 --- p.39 / Chapter 2. --- "The structure of [Li(CHPhC5H4N-2)(tmeda)]2-tmeda, 36.tmeda" --- p.43 / Chapter 3. --- The Structure of [Li{CPh(SiMe3)C5H4N-2}(tmeda)] 38 --- p.46 / Chapter 4. --- Structure of [Li{CH(SiButMe2)C5H4N-2} (Et2O)]2 39 --- p.49 / Chapter 5. --- "Comparison of Structural Data of Lithium Complexes 34, 36, 38, and 39" --- p.52 / Chapter 1.3. --- Experimental Section --- p.60 / References --- p.64 / Chapter CHAPTER2 --- SYNTHESES AND STRUCTURES OF ORGANOTIN COMPLEXES WITH β- FUNCTIONALISED ALKYL LIGANDS --- p.67 / Chapter 2.1 --- Introduction --- p.67 / Chapter 2.1.1 --- A general Review of Divalent Tin Alkyl Chemistry --- p.67 / Chapter 2.1.2 --- Structures of Some Sn(II) compounds --- p.69 / Chapter 2.1.3 --- Reactivities of Dialkyltin Compounds --- p.71 / Chapter 2.1.4 --- General View on Hypervalent Organotin Chemistry --- p.72 / Chapter 2.2 --- Results and discussion --- p.76 / Chapter 2.2.1 --- Synthesis of Low-valent Tin Complexes with the β N-Functionalised Alkyl Ligands --- p.76 / Chapter 2.2.2 --- NMR Spectra of Tin(II) Alkyl Complexes --- p.78 / Chapter 1. --- NMR Spectra of [Sn{CH(SiButMe2)C5H4N-2}3][Li(tmeda)Cl}2] 77 --- p.78 / Chapter 2. --- 1H NMR spectrum of [Sn{CH(SiButMe2)C5H4N-2} Cl]2 78 --- p.80 / Chapter 3. --- lH NMR Spectrum of Product from the Reaction of [{CH(SiButMe2)C5H4N-2}Cl] 2 78 and [Li {CH(SiButMe2)C5H4N-2} (tmeda)]2 34 --- p.80 / Chapter 4. --- 1H NMR Spectrum of Compound [Sn{CPh(SiMe3)C5H4N-2}2] 79 --- p.84 / Chapter 5. --- 119Sn NMR Spectra of Tin(II) Compounds with Ligand anionic {CH(SiButMe2)C5H4N-2}- --- p.84 / Chapter 2.2.3 --- "Syntheses of Sn(IV) Compounds Sn(CRR 'C5H4N)R"" 2X" --- p.84 / Chapter 2.2.4 --- NMR Characterization of Sn(CRR ´ة C5H4N)R2X (X= Cl or Br) --- p.85 / Chapter 1. --- NMR Spectra of Compound Sn{CH(SiButMe2)C5H4N-2}But2Cl 85 --- p.85 / Chapter 2. --- 1H NMR Spectrum of Compound [Sn{CPh(SiMe3)C5H4N-2}Me2Br 86 --- p.89 / Chapter 3. --- 119Sn NMR Spectra of Compounds [Sn{CH(SiButMe2)(C5H4N-2}But2Cl] 85 and [Sn{CPh(SiMe3)C5H4N- 2}Me2Br 86 --- p.89 / Chapter 4. --- Mass Spectra of Compounds [Sn{CH(SiButMe2)C5H4N-2}But2Cl ] 85 and [Sn{CPh(SiMe3)C5H4N- 2}Me2Br] 86 --- p.90 / Chapter 2.2.5 --- "The Structure of Tin (II) Alkyl Complexes [Sn{CH(SiButMe2)C5H4N-2}3] - [Li {Li (tmeda) Cl} 2]77, [Sn{CH(SiButMe2)C5H4N-2}Cl]2 78 , and [Sn{CPh(SiMe3)C5H4N-2}2] 79" --- p.91 / Chapter 1. --- The Structure of Lithium Trialkylstannate(II) Complex --- p.91 / Chapter 2. --- The Molecular Structure of [Sn{CH(SiButMe2)C5H4N-2}Cl]2 78 --- p.96 / Chapter 3. --- The Structure of Complex[Sn{CPh(SiMe3)C5H4N-2}2] 79 --- p.99 / Chapter 4. --- Comparison of Structures of Divalent Tin Alkyl Complexes --- p.102 / Chapter 2.2.6 --- The Structure of Sn(pic?)R2X (X = Cl or Br --- p.105 / Chapter 1. --- The Structure of [2- {t-butyldimethylsilyl)methylene}pyridyl]-di(t-butyl)tin Chloride 85 --- p.105 / Chapter 2. --- The Molecular Structure of [Sn{CPh(SiMe3)C5H4N-2}Me2Br] 86 --- p.108 / Chapter 2.3 --- Experimental --- p.110 / Chapter 2.3.1 --- Syntheses of Subvalent Tin Alkyl Compounds --- p.110 / Chapter 2.3.2 --- Synthesis of Tetravalent-Tin Complexes with Substituted Methyl Pyridine Ligand --- p.112 / REFERENCES --- p.114 / Chapter CHAPTER3 --- TRANSITION METAL DERIVATIVES WITH β-FUNCTIONALIZED ALKYL LIGAND --- p.117 / Chapter 3.1 --- Introduction --- p.117 / Chapter 3.1.1 --- The Decomposition Pathways of Organometallic Compounds --- p.117 / Chapter 3.1.2 --- Iron (II) and Cobalt (II) Alkyl Complexes --- p.119 / Chapter 3.1.3 --- Homoleptic Iron(II) and Cobalt(II) Alkyls --- p.119 / Chapter 3.2 --- Results and Discussion --- p.121 / Chapter 3.2.1 --- Syntheses of M(II) (M = Fe or Co) N-functionalized Alkyl Complexes --- p.121 / Chapter 1. --- The reaction of MC12 with [Li {CH(SiButMe2)C5H4N-2}(tmeda)]2 34 --- p.121 / Chapter 2 --- The reaction of MC12 with [Li {CPh(SiMe3)C5H4N-2} (tmeda)] 38 --- p.123 / Chapter 3. --- The Reaction of [CPh2C5H4N]- with S and Synthesis of Complex [Ni{SC(Ph)2C5H4N}2] 119 --- p.127 / Chapter 3.2.2 --- Characterization of Iron (II) and Cobalt (II) Alkyl Complexes --- p.128 / Chapter 1. --- The Magnetic Properties of Compounds [Co {CPh(SiMe3)C5H4-2} 2] 113 and [Fe{CPh(SiMe3)C5H4- 2}(tmeda)Cl] 115 --- p.128 / Chapter 2. --- Mass Spectra of the Iron(II) and Cobalt(II) Compounds --- p.128 / Chapter 3.2.3 --- The X-ray Structures of the Complexes --- p.129 / Chapter 1. --- Structure of [Fe{CH(SiButMe2)C5H4N-2}2]2109 --- p.129 / Chapter 2. --- Structure of complex [Co{CH(SiButMe2)C5H4N-2}2]2110 --- p.132 / Chapter 3. --- Structure of Compound [Co{CPh(SiMe3)C5H4N-2}2] 113 --- p.135 / Chapter 4. --- The Structure of Compound [Fe {CPh(SiMe3)C5H4N-2} (tmeda)Cl] 115 --- p.138 / Chapter 5. --- "Comparison of the structures of the iron(II) and cobalt(II) alkyls 109，110, 113 and 115" --- p.140 / Chapter 3.2.4 --- The Structure of Complex [Ni{SC(Ph)2C5H4N}2] 119 --- p.142 / Chapter 3.3 --- Experimental --- p.145 / REFERENCES --- p.148 / Chapter CHAPTER4 --- ZIRCONOCENE DERIVATIVES WITH THE SUBSTITUTED METHYL PYRIDINE LIGANDS --- p.150 / Chapter 4.1 --- Introduction --- p.150 / Chapter 4.1.1 --- A General Review of Zirconocene Derivatives --- p.150 / Chapter 4.2.1 --- Syntheses of Zirconocene Compounds Cp2Zr(CRR ´ةC5H4N)Cl --- p.152 / Chapter 4.2.2 1 --- H NMR spectra of Cp2Zr(CRR ´ةC5H4N)Cl --- p.153 / Chapter 4.2.3 --- The Molecular Structure of [ZrCp2(CPh2C5H4N-2)Cl] 127 --- p.156 / Chapter 4.3 --- Experimental --- p.160 / REFERENCES --- p.162 / APPENDIX A: PHYSICAL MEASUREMENTS AND TABLES OF CRYSTAL DATA AND REFINEMENT PARAMETERS --- p.163 / APPENDIX B: TABLES OF ATOMIC COORDINATES AND THERMAL PARAMETERS --- p.172

by Mok-Yin Chow. / Thesis (M.Phil.)--Chinese University of Hong Kong, 1992. / Includes bibliographical references (leaves 55-58). / Acknowledgement --- p.1 / Abstract --- p.2 / Contents --- p.3 / List of Figures --- p.4 / List of Tables --- p.5 / Chapter 1. --- Introduction --- p.6 / Chapter I. --- Chemistry of pseudohalides --- p.6 / Chapter II. --- Infrared spectroscopy of pseudohalides --- p.8 / Chapter III. --- Chemistry of metal carboxylates --- p.10 / Chapter IV. --- Infrared spectroscopy of carboxylates --- p.13 / Chapter V. --- Chemistry of betaine ligands --- p.14 / Chapter VI. --- Objectives of this research --- p.15 / Chapter 2. --- Experimental --- p.17 / Chapter I. --- Preparation --- p.17 / Chapter II. --- X-ray crystallography --- p.21 / Chapter 3. --- Results and discussion --- p.23 / Chapter I. --- "Isostructural complexes Co2(bet)2(N3)4 1,Zn2(bet)2(N3)42, Cd2(bet)2(N3)4 3, and Cd2(bet)2(NCO)4 4" --- p.23 / Chapter II. --- Copper(II) complex Cu2(bet)2(N3)2(N03)2 5 --- p.29 / Chapter III. --- Cadmium(II) complexes Cd3(bet)4(SCN)6(H20)2 6 and Cd(prbet)(NCS)2 7 --- p.34 / Chapter IV. --- Barium(II) complex Ba(pybet)2(NCS)2 8 --- p.43 / Chapter V. --- Cobalt(II) complex [Co(pybet)2(NCS)(H20)3]2[Co(NCS)4] 9 --- p.49 / Chapter VI. --- Conclusion --- p.53 / References --- p.55 / Publications based on work reported in this thesis --- p.59 / Appendix --- p.60

by Xiao-Ming Chen. / Thesis (Ph.D.)--Chinese University of Hong Kong, 1992. / Includes bibliographical references (leaves 127-135). / Acknowledgements / Abstract --- p.i / Nomenclature --- p.ii / Table of Contents --- p.iii / List of Tables --- p.iv-v / List of Figures --- p.v-vii / Chapter 1. --- Introduction --- p.1-9 / Chapter 2. --- Results and Discussion --- p.10-104 / Chapter 1. --- Betaine derivatives --- p.10-19 / Chapter 2. --- "Complexes of manganese(II), cobalt(II), and nickel(II)" --- p.20-31 / Chapter 3. --- Complexes of zinc(II) --- p.32-40 / Chapter 4. --- Complexes of cadmium(II) and mercury(II) --- p.41-56 / Chapter 5. --- Complexes of silver(I) --- p.57-76 / Chapter 6. --- Complexes of copper(II) --- p.77-97 / Chapter 7. --- Mixed-metal complexes --- p.98-104 / Chapter 3. --- Conclusions --- p.105-106 / Chapter 4. --- Experimental --- p.107-126 / Chapter 5. --- References --- p.127-135 / Chapter 6. --- Appendix A --- p.136-151 / Chapter 1. --- Atomic coordinates and equivalent isotropic thermal parameters --- p.136-144 / Chapter 2. --- Anisotropic thermal parameters --- p.145-151 / Chapter 7. --- Appendix B (in a separated volume to be kept as Supplementary Data in the Department of Chemistry) Tables of structure factors

by De-Dong Wu. / Publication date from spine. / Thesis (Ph.D.)--Chinese University of Hong Kong, 1995. / Includes bibliographical references (leaves 175-184). / Acknowledgment --- p.i / Abstract --- p.ii / Table of Contents --- p.iii / List of Tables --- p.iv / List of Figures --- p.v / Chapter 1. --- Introduction --- p.1 / Chapter 1.1. --- The Chemistry of Coordination Polymers --- p.1 / Chapter 1.2. --- Generation of Coordination Polymeric Structures --- p.2 / Chapter 1.3. --- Research Strategy --- p.7 / Chapter 2. --- Description of Crystal Structures --- p.15 / Chapter 2.1. --- The Double Betaine Compounds --- p.15 / Chapter 2.2. --- Complexes of Silver(I) --- p.39 / Chapter 2.3. --- Complexes of Cadmium(II) --- p.60 / Chapter 2.4. --- Complexes of Mercury(II) --- p.89 / Chapter 2.5. --- Complexes of Copper(II) and Sodium(I) --- p.113 / Chapter 3. --- Summary and Discussion --- p.127 / Chapter 3.1. --- Generation of Coordination Polymeric Structures --- p.127 / Chapter 3.2. --- Coordination Modes of Double Betaines --- p.132 / Chapter 3.3. --- Conformation of the Double Betaines --- p.135 / Chapter 3.4. --- Synthesis of Betaine Compounds --- p.139 / Chapter 4. --- Experimental --- p.150 / Chapter 4.1. --- Preparation --- p.150 / Chapter 4.2. --- Physical Measurements --- p.164 / Chapter 4.3. --- Crystallography --- p.164 / Chapter 5. --- References --- p.175 / Appendix --- p.185 / Chapter 1. --- Atomic coordinates and equivalent isotropic thermal parameters --- p.185 / Chapter 2. --- Anisotropic thermal parameters --- p.196 / Chapter 3. --- H-atom coordinates and isotropic thermal parameters --- p.203

by Chan Chun-Chung, Jerry. / The "59" in Co in title is superscript. / Thesis (Ph.D.)--Chinese University of Hong Kong, 1996. / Includes bibliographical references (leaves 157-170). / DESCRIPTIVE NOTE --- p.iii / Chapter CHAPTER ONE: --- A BRIEF SURVEY OF TRANSITION METAL NMR STUDIES --- p.1 / Chapter 1.0 --- Introduction --- p.1 / Chapter 1.1 --- Solution NMR Of Transition Metals --- p.2 / Chapter 1.1.1 --- Parametrization Model of Chemical Shifts --- p.4 / Chapter 1.2 --- Theoretical Calculation of the Chemical Shielding Constants of Transition Metals --- p.6 / Chapter 1.3 --- Solid State NMR of Transition Metals --- p.7 / Chapter 1.4 --- Scope of the Thesis --- p.9 / Chapter CHAPTER TWO: --- THEORY AND BACKGROUND --- p.10 / Chapter 2.0 --- Introduction --- p.10 / Chapter 2.1 --- The Origin of Chemical Shielding --- p.10 / Chapter 2.1.1 --- The Ramsey Shielding Tensor Equation with Gauge Origin Chosen at the Nucleus --- p.13 / Chapter 2.1.2 --- The Ramsey Shielding Tensor Equation with Arbitrary Gauge Origin --- p.20 / Chapter 2.1.3 --- The Physical Picture Associated with the Ramsey Shielding Equation --- p.21 / Chapter 2.2 --- Ab Initio Shielding Calculation --- p.24 / Chapter 2.2.1 --- Coupled Hartree-Fock Method --- p.25 / Chapter 2.2.2 --- Gauge Dependence Problem --- p.27 / Chapter 2.2.3 --- Post Hartree-Fock Methods --- p.29 / Chapter 2.3 --- Density Functional Theory --- p.30 / Chapter 2.3.1 --- The Hohenberg-Kohn Theorems --- p.30 / Chapter 2.3.2 --- The Kohn-Sham Approach --- p.35 / Chapter 2.3.3 --- Approximation to the Exchange- Correlation Energy --- p.37 / Chapter CHAPTER THREE: --- INTERPRETATION OF 59Co NMR SHIELDING USING THE HARD AND SOFT ACID-BASE CONCEPT -- INSIGHT INTO THE RELATIVE MAGNITUDE OF THE NEPHELAUXETIC AND THE SPETROCHEMICAL EFFECT --- p.39 / Chapter 3.0 --- Introduction --- p.39 / Chapter 3.1 --- Theory --- p.42 / Chapter 3.2 --- Evaluation of the Model --- p.45 / Chapter 3.3 --- Application to the Studies of trans-[Co(en)2X2](3+2n) + in Different Solvents and the Determination of the Spectrochemical Trend --- p.54 / Chapter 3.4 --- "Simultaneous Determination of the Nuclear Quadrupole Coupling Constant, Chemical Shift Anisotropy and Rotational Correlation Time in trans-Na[Co(acac)2(NO2)2]， trans- [Co(acac)2(NH3)2 ]I, trans-[Co(acac)2(CH3NH2)2]I and trans-[Co(acac)2(NH3)(NO2)]" --- p.59 / Chapter 3.5 --- Summary --- p.64 / Chapter CHAPTER FOUR: --- DENSITY FUNCTIONAL STUDY OF THE ELECTRONIC STRUCTURES OF [Co(NH3)5X](3+n)+ USING DIFFERENT POPULATION AND BONDING ANALYSIS METHODS --- p.66 / Chapter 4.0 --- Introduction --- p.66 / Chapter 4.1 --- Computational Details --- p.69 / Chapter 4.2 --- Bond Covalency Analysis of [Co(NH3)5X](3+n)+ --- p.71 / Chapter 4.2.1 --- Mayer Bond Order Analysis --- p.71 / Chapter 4.2.2 --- Natural Population Analysis --- p.73 / Chapter 4.2.3 --- Natural Bond Orbital Analysis --- p.76 / Chapter 4.2.4 --- Mulliken Population Analysis --- p.82 / Chapter 4.3 --- Summary --- p.86 / Chapter CHAPTER FIVE: --- DENSITY FUNCTIONAL STUDY OF 59Co CHEMICAL SHIELDING CONSTANTS --- p.87 / Chapter 5.0 --- Introduction --- p.87 / Chapter 5.1 --- SOS-DFPT-IGLO Calculations of 59Co NMR Shielding Parameters of Hexacoordinated Diamagnetic Co(III) Complexes --- p.90 / Chapter 5.1.1 --- Computational Details --- p.91 / Chapter 5.1.2 --- Basis Sets and XC Functional for 59Co Shielding Calculations --- p.92 / Chapter 5.1.2.1 --- 59Co NMR Shielding Calculation of [Co(CN)6]3- --- p.92 / Chapter 5.1.2.2 --- Nearest Neighbour Effect --- p.94 / Chapter 5.1.3 --- Comparison of the Calculated and Experimental 59Co Chemical Shift Anisotropy and Asymmetry Factor --- p.95 / Chapter 5.1.4 --- Comparison of the Calculated and Experimental 59Co Isotropic Chemical Shifts --- p.97 / Chapter 5.1.4.1 --- Reproducing the Experimental Trend by SOS-DFPT-IGLO? --- p.99 / Chapter 5.1.4.2 --- Local and Non-local Paramagnetic Shielding Contributions --- p.103 / Chapter 5.1.5 --- General Comments of the Calculated Results --- p.104 / Chapter 5.2 --- A Comparative Study of the Calculation of 59Co NMR Shielding Constants of Hexacoordinated Diamagnetic Co(III) Complexes Using SOS-DFPT-IGLO and Hybrid DFT-GIAO Methods --- p.105 / Chapter 5.2.1 --- Computational Details --- p.106 / Chapter 5.2.2 --- Comparison of DFT-IGLO-Becke/Perdew and DFT-GIAO-Becke/Perdew --- p.106 / Chapter 5.2.3 --- DFT-GIAO-B3LYP --- p.108 / Chapter 5.2.4 --- Summary --- p.111 / Chapter CHAPTER SIX: --- STUDY OF THE SHIELDING CONSTANTS OF DIAMAGNETIC HEXACOORDINATED Co(III) COMPLEXES BY POLYCRYSTALLINE 59Co NMR AND DENSITY FUNCTIONAL THEORY --- p.112 / Chapter 6.0 --- Introduction --- p.112 / Chapter 6.1 --- Solid State NMR Technique for Quadrupolar Nuclei --- p.112 / Chapter 6.2 --- Static Powder Lineshape Analysis --- p.114 / Chapter 6.2.1 --- Excitation of Quadrupolar Nuclei --- p.114 / Chapter 6.2.1.1 --- Selective and Partially Selective Excitation --- p.116 / Chapter 6.2.2 --- Spin Echo Pulse Sequence --- p.117 / Chapter 6.2.3 --- Lineshape Simulation --- p.120 / Chapter 6.3 --- Solid State 59Co NMR Study of Hexacoordinated Co(III) Complexes --- p.124 / Chapter 6.3.1 --- Experimental --- p.124 / Chapter 6.3.2 --- Simulation Details --- p.125 / Chapter 6.3.2.1 --- [Co(NH3)4CO3]NO3 --- p.127 / Chapter 6.3.2.2 --- [Co(en)2CO3]Cl and [Co(en)2NO3](NO3)2 --- p.130 / Chapter 6.3.2.3 --- cis-[Co(en)2(N02)2]NO3 and cis-[Co(en)2(N3)2]NO3 --- p.133 / Chapter 6.3.2.4 --- K3[Co(CN)6] --- p.133 / Chapter 6.3.2.5 --- "Co(acac)3， K3[Co(NO2)6] and [Co(en)3]X3 (X = C1, Br, I)" --- p.137 / Chapter 6.4 --- Dependence of 59Co Shielding Calculation on Basis Sets and Exchange Correlation Functional --- p.143 / Chapter 6.4.1 --- CSA and η calculations of [Co(NH3)4C03] Br --- p.144 / Chapter 6.4.2 --- CSA and η Calculations of [Co(NH3)6]C13 --- p.147 / Chapter 6.4.3 --- Shielding Calculations of Larger Co(III) Complexes at B3PW91/6311+G* Level --- p.149 / Chapter 6.5 --- Summary --- p.153 / Chapter CHAPTER SEVEN: --- CONCLUSION AND FUTURE WORK --- p.154 / BIBLIOGRAPHY --- p.157 / APPENDIX A MATHEMATICAL DETAILS FOR THE DERIVATION OF THE RAMSEY SHIELDING EQUATION --- p.171 / APPENDIX B ANALYSIS OF THE SIGN OF PARAMAGNETIC AND DIAMAGNETIC SHIELDING --- p.178 / APPENDIX C GENERALIZATION OF EQUATION [3.4] TO INCLUDE THE EFFECT OF π-BONDING --- p.181 / APPENDIX D GEOMETRY OPTIMIZATION OF CoH AND CoO --- p.183 / APPENDIX E A NON-LINEAR ITERATIVE LEAST SQUARE FITTING PROCEDURE FOR THE ANALYSIS OF SOLID STATE NMR STATIC SPECTRUM OF QUADRUPOLAR NUCLEUS --- p.187