by Au Yeung Ho Yu. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2006. / Includes bibliographical references. / Abstracts in English and Chinese. / Abstract --- p.i / 摘要 --- p.iii / Acknowledgement --- p.v / Table of Contents --- p.vi / Abbreviations --- p.ix / List of Compounds --- p.x / Chapter Chapter 1 --- A General Introduction To Late Transition Metal Amides / Chapter 1.1 --- General Background --- p.1 / Chapter 1.2 --- An Overview of Late Transition Metal Amides --- p.2 / Chapter 1.3 --- Objectives of This Work --- p.7 / Chapter 1.4 --- References for Chapter1 --- p.9 / Chapter Chapter 2 --- Late Transition Metal Complexes Derived From 2-Pyridyl Amido Ligand / Chapter 2.1 --- General Background / Chapter 2.1.1 --- A Brief Introduction to Pyridine-Functionalized Amido Ligands --- p.13 / Chapter 2.1.2 --- Late Transition Metal Complexes Supported by 2-Pyridyl Amido Ligands --- p.14 / Chapter 2.2 --- Aims of Our Study --- p.18 / Chapter 2.3 --- Result and Discussion / Chapter 2.3.1 --- Preparation of the [N(CH2But)(2-C5H3N-6-Me)]- Ligand and the Corresponding Lithium Derivatives --- p.19 / Chapter 2.3.2 --- Syntheses and Structures of Iron(II) and Cobalt(II) Amides / Chapter 2.3.2.1 --- "Synthesis of [M(L1)2(HL1)] [M = Fe (6), Co (7)]" --- p.20 / Chapter 2.3.2.2 --- Physical Characterization of Compounds 6 and7 --- p.24 / Chapter 2.3.2.3 --- Molecular Structures of Compounds 6 and7 --- p.24 / Chapter 2.4 --- Experimentals for Chapter 2 --- p.31 / Chapter 2.5 --- References for Chapter 2 --- p.34 / Chapter Chapter 3 --- Synthetic and Structural Studies of Late Transition Metal Anilides / Chapter 3.1 --- An Overview on Anilido Complexes --- p.40 / Chapter 3.2 --- Aims of Our Study --- p.45 / Chapter 3.3 --- Result and Discussion / Chapter 3.3.1 --- Aniline Precursors and The Lithium Derivatives / Chapter 3.3.1.1 --- Syntheses of the Aniline Precusors HLn (n = 2-5) --- p.46 / Chapter 3.3.1.2 --- Syntheses of Lithium Derivatives of Ln (n = 2-5) --- p.47 / Chapter 3.3.1.3 --- Physical Characterization of Compounds 11-13 --- p.48 / Chapter 3.3.1.4 --- "Molecular Structures of Compounds 11a, 12a and 12b" --- p.49 / Chapter 3.3.2 --- Syntheses and Structures of Late Transition Metal Anilides / Chapter 3.3.2.1 --- Syntheses of N-Silylated Anilides --- p.57 / Chapter 3.3.2.2 --- Physical Characterization of Compounds 14-20 --- p.64 / Chapter 3.3.2.3 --- Molecular Structures of Compounds 14-20 --- p.65 / Chapter 3.3.2.4 --- Syntheses of N-Alkylated Anilides --- p.89 / Chapter 3.3.2.5 --- Physical Characterization of Compounds 21-26 --- p.92 / Chapter 3.3.2.6 --- "Molecular Structures of Compounds 21, 23, 25 and 26" --- p.93 / Chapter 3.4 --- Experimentals for Chapter 3 --- p.103 / Chapter 3.5 --- References for Chapter 3 --- p.112 / Chapter Chapter 4 --- Reactions of Late Transition Metal Anilides and Their Derivatives / Chapter 4.1 --- General Background / Chapter 4.1.1 --- Reactions of Late Transition Metal Amides --- p.124 / Chapter 4.1.2 --- A Brief Introduction to Oxidative Coupling of Phenols --- p.129 / Chapter 4.1.3 --- A Brief Overview on the Ring-Opening Polymerization of Cyclic Esters --- p.130 / Chapter 4.2 --- Aims of Our Study --- p.132 / Chapter 4.3 --- Results and Discussion / Chapter 4.3.1 --- Reactions of Late Transition Metal Anilides and Their Derivatives / Chapter 4.3.1.1 --- Ligand Substitution --- p.133 / Chapter 4.3.1.2 --- Chloride Abstraction --- p.137 / Chapter 4.3.1.3 --- Chemical Reduction --- p.138 / Chapter 4.3.1.4 --- Reaction with Unsaturated Compounds --- p.139 / Chapter 4.3.1.5 --- Physical Characterization of Compounds 27-33 --- p.140 / Chapter 4.3.1.6 --- Molecular Structures of Compounds 27-33 --- p.142 / Chapter 4.3.2 --- Oxidation of Bisaryloxide Complexes --- p.162 / Chapter 4.3.3 --- The Ring-Opening Polymerization of e-Caprolactone --- p.167 / Chapter 4.4 --- Experimentals for Chapter 4 --- p.171 / Chapter 4.5 --- References for Chapter 4 --- p.176 / "Appendix 1 General Procedures, Physical Measurements and X-Ray Structure Analysis" --- p.187 / Appendix 2 NMR Spectra of Compounds --- p.189 / Appendix 3 Selected Crystallographic Data --- p.202

by Fuquan Song. / Thesis (Ph.D.)--Chinese University of Hong Kong, 1998. / Includes bibliographical references (p. 204-205). / 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.

This thesis explores the synthesis, characterization, and reactivity of main group and transition metal complexes that feature ligands with carbon, sulfur, and selenium donor atoms. Specifically, the carbon donor ligands explored include the carbodiphosphorane, (Ph3P)2C, and the analytical reagent, nitron, which behaves like an N-heterocyclic carbene in solution. The sulfur ligands include the amino acids cysteine and glutathione, and the tripodal tris(2-mercapto-1-t-butylimidazolyl)hydroborato ligand, of which the latter provides an [S3] coordination environment. Finally, the selenium donor ligands explored comprise the phenylselenolate, [PhSe]–, and the selenobenzimidazole, H(sebenzimMe). Chapter 1 investigates the chemistry of two-coordinate mercury alkyl complexes supported by sulfur and selenium ligands. The first part of Chapter 1 examines the structure of the amino acid complexes, (Cys)HgMe and (GS)HgMe, which indicate that both complexes possess linear geometries. Additionally, 1H NMR studies confirm the labile nature of the cysteinato ligand in (Cys)HgMe. More specifically, in the presence of excess cysteine, exchange is observed, a result that is of relevance to mercury toxicity and detoxification. The second part of Chapter 1 examines the exchange reactions of the phenylselenolate mercury alkyl complexes, PhSeHgR (R = Me, Et), as well as their propensity to undergo protolytic Hg–C bond cleavage. The results from these experiments indicate that coordination by selenium promotes protolytic cleavage of Hg–C bonds more rapidly than compared to the sulfur analogues. Expanding the metal centers to include the lighter group 12 metals, Chapter 2 investigates ligand exchange between zinc, cadmium, and mercury in a sulfur-rich coordination environment as provided by the [S3] tris(2-mercapto-1-t-butylimidazolyl)hydroborato ligand. Similar to the Schlenk equilibrium, alkyl group exchange between the same metal center is observed as demonstrated by the formation of [TmBut]MMe via treatment of [TmBut]2M with Me2M (M = Zn, Cd). Additionally, alkyl group exchange between different metals centers is also possible. For example, a mixture of [TmBut]ZnMe and Me2Cd form an equilibrium mixture with [TmBut]CdMe and Me2Zn. Furthermore, transfer of the [TmBut] ligand between the metal centers is possible too. This is demonstrated by the transfer of [TmBut] from mercury to zinc in the methyl system, [TmBut]HgMe/Me2Zn. Additionally, transfer of [TmBut] from zinc to mercury is also observed upon treatment of [TmBut]2Zn with HgI2 to afford [TmBut]HgI and [TmBut]ZnI, thereby indicating that the nature of the co-ligand has a profound effect on the thermodynamics of ligand exchange. Chapter 3 explores the coordination chemistry of the selenium donor ligand, H(sebenzimMe). H(sebenzimMe) is able to coordinate metal centers through the selenium atom in a dative fashion, and, depending upon the metal center, up to four H(sebenzimMe) ligands can coordinate the same metal. Additionally, H(sebenzimMe) can be deprotonated to form [sebenzimMe]–, allowing for the potential of an LX coordination mode, which results in bridging complexes for the metal compounds investigated. In regards to the metal centers investigated in Chapter 3, H(sebenzimMe) has been demonstrated to be an effective ligand for Pd, Ni, Zn and Cd. Chapter 4 investigates the various structural polymorphs of the carbodiphosphorane, (Ph3P)2C. More specifically, previous crystal structures of (Ph3P)2C have demonstrated that the P–C–P bond angle is highly bent. This is consistent with simple VSEPR theory, which predicts a bent geometry for compounds possessing a coordination number of two and two lone pairs of electrons. However, Chapter 4 details the characterization of a new linear form of (Ph3P)2C. DFT calculations indicate that the energy required to bend the P–C–P bonds of (Ph3P)2C over the range of 130˚-180˚ is less than 1.0 kcal mol–1. Analysis of the Natural Localized Molecular Orbitals (NLMOs) indicates that upon bending of the P–C–P bond angle, the -type lone pair NLMO on the central carbon atom is stabilized, while the two P–C bonding orbitals NLMOs are destabilized. The differential behavior of the lone-pair and bonding orbitals upon bending is one component that provides a simple rationalization for the flexibility of (Ph3P)2C. In view of the fact that carbodiphosphoranes possess two lone pairs of electrons on the central carbon atom, (Ph3P)2C is an effective ligand for a variety of metals and nonmetals. Chapter 5 investigates the reactivity of (Ph3P)2C towards the main group alkyl metal complexes, Me3E (E = Al, Ga), Me2M (M = Mg, Zn, Cd), and MeHgI, as well as Mg[N(TMS)2]2. Additionally, the reactivity of (Ph3P)2C towards transition metal complexes was also investigated. (Ph3P)2C is capable of coordinating in several different ways, a couple of which include forming a Lewis acid/base adduct, and ortho metalation of one of the phenyl groups. Lastly, Chapter 6 expands the coordination chemistry of nitron. Nitron, which is used as a quantitative analytical reagent, has recently been shown to behave like an NHC in solution. This is attributed to the presence of the carbenic tautomer of nitron when placed in solution. Thus, nitron effectively coordinates metal centers through the central carbon atom. Chapter 6 outlines (i) the synthesis and structural characterization of nickel, palladium, and iridium complexes that feature nitron as a ligand, and (ii) the ability of the corresponding iridium complexes to serve as catalysts for the dehydrogenation of formic acid and the hydrosilylation of aldehydes.

Sze Wing Yin. / Thesis submitted in: November 2005. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2006. / Includes bibliographical references. / Abstracts in English and Chinese. / Table of Contents --- p.vi / Acknowledgements --- p.i / Abstract --- p.ii / 摘要 --- p.iv / List of Compounds Synthesized --- p.x / Abbreviation --- p.xi / Chapter Chapter 1 --- Syntheses and Characterization of Bis(phosphoranoimido)lithium and Late Transition Metal Complexes / Chapter 1.1 --- Introduction --- p.1 / Chapter 1.1.1 --- A General Review of Bis(Phosphoranoimido) Ligands --- p.1 / Chapter 1.1.2 --- Synthesis of Bis(Phosphoranoimido)metal Complexes --- p.8 / Chapter 1.2 --- Objectives --- p.13 / Chapter 1.3 --- Results and Discussion --- p.14 / Chapter 1.3.1.1 --- "Synthesis of Bis(Phosphoranoimido)lithium complexes [Li{{(Me3SiNPR2CH)(Me3SiN=PR2CH2)}C5H3N-2，6} (R = Ph, 36; R = Pr', 37)]" --- p.14 / Chapter 1.3.1.2 --- Spectroscopic Properties of Complexes 36 and 37 --- p.14 / Chapter 1.3.1.3 --- "Molecular Structures of [Li{{(Me3SiNPR2CH)- (Me3SiN=PR2CH2)}C5H3N-2,6} (R = Ph, 36; R = Pr', 37)]" --- p.16 / Chapter 1.3.2.1 --- Synthesis and Characterization of Bis(Phosphoranoimido)transition Metal Complexes --- p.21 / Chapter 1.3.2.2 --- Spectroscopic Properties of 38 - 41 --- p.21 / Chapter 1.3.2.3 --- "Molecular Structures of [MCI {{(Me3SiNPPh2CH)- (Me3SiN=PPh2CH2)}C5H3N-2,6}] (M = Co, 38; Mn, 39)， [MnCl{{(Me3SiNPPri2CH)(Me3SiN=PPri2CH2)}C5H3N-2，6}] (41)" --- p.22 / Chapter 1.4 --- Experimental Section --- p.31 / Chapter 1.5 --- References for Chapter 1 --- p.36 / Chapter Chapter 2 --- Syntheses and Characterization of Bis(phosphoranoimido)zirconium(IV) Complex / Chapter 2.1 --- Introduction --- p.39 / Chapter 2.1.1 --- General Aspects of Group 4 Metal Complexes --- p.39 / Chapter 2.2 --- Results and Discussion --- p.44 / Chapter 2.2.1 --- "Synthesis and Characterization of Bis(phosphoranoimido)zirconium(IV) Complex [Zr{(Me3SiNPPh2C)(Me3SiN=PPh2CH2)C5H3N-2,6}(NMe2)2] (46)" --- p.44 / Chapter 2.2.2 --- Reaction of Bis(phosphoranoimido)zirconium(IV) Complex (46) with HC1 --- p.45 / Chapter 2.2.3 --- Spectroscopic Properties of Complex 46 --- p.45 / Chapter 2.2.4 --- Molecular Structure of [Zr{(Me3SiNPR2C)- (Me3SiN=PR2CH2)5H3N-2，6}(NMe2)2] (46) --- p.46 / Chapter 2.3 --- Experimental Section --- p.51 / Chapter 2.4 --- References for Chapter 2 --- p.52 / Chapter Chapter 3 --- Syntheses and Characterization of Bis(phosphoranoimido)samarium(III) Complexes / Chapter 3.1 --- Introduction --- p.54 / Chapter 3.1.1 --- A General Review of Lanthanide Complexes --- p.54 / Chapter 3.1.2 --- General Aspect of Bis(phosphoranoimido)lanthanide Metal Complexes --- p.58 / Chapter 3.1.3 --- Synthesis and Structure of Bis(phosphoranoimido)dilithium Complex --- p.60 / Chapter 3.2 --- Results and Discussion --- p.63 / Chapter 3.2.1 --- Synthesis and Characterization of Bis(phosphoranoimido)samarium(III) Complexes --- p.63 / Chapter 3.2.2 --- Spectroscopic Properties of 56 and 57 --- p.65 / Chapter 3.2.3 --- "Molecular Structures of [Sm {{(Me3SiNPPh2CH)2} - C5H3N-2，6}(μ-Cl2)Li(THF)2] (56) and [Sm{{(Me3SiNPPri2CH)2}C5H3N-2,6}2(μ-Cl)]2 (57)" --- p.65 / Chapter 3.3 --- Experimental Section --- p.72 / Chapter 3.4 --- References for Chapter 3 --- p.74 / Appendix I / Chapter A. --- General Procedures --- p.77 / Chapter B. --- Physical and Analytical Measurements --- p.77 / Appendix II / Table A.1. Selected Crystallographic Data for Compounds 36，37 and 38 --- p.80 / Table A.2. Selected Crystallographic Data for Compounds 39，41 and 46 --- p.81 / Table A.3. Selected Crystallographic Data for Compounds 56 and 57 --- p.82

Chan, Ka Wai. / "May 2008." / Thesis (Ph.D.)--Chinese University of Hong Kong, 2008. / Includes bibliographical references (p. 160-169). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstracts in English and Chinese.

[eta5:sigma-Me2C(C5H4 )(C2B10H10]Zr[eta2-S 2C2B10H10](NHMe2)2 was prepared by amine elimination reaction between [eta5:sigma-Me 2C(C5H4)(C2B10H10)]Zr[NMe 2)2 and 1,2-(HS)2-1,2-C2B10 H10. It underwent ligand substitution reaction with XylNC to generate [eta5:sigma-Me2C(C5H 4)(C2B10H10]Zr[eta2-S 2C2B10H10][2,6-(CH3) 2C6H3N=C]2 and reacted with THE to give ring opening product [eta5:sigma-Me2C(C 5H4)(C2B10H10]ZR-[eta 2-S2C2B10H10][sigma-O(CH 2)4NHMe2)]. Zirconium-promoted nucleophilic reaction of dimethylamine with various kinds of unsaturated polar organic substrates, such as PhCN, PhNCO, nBuNCS and MA were studied. / Direct deboration of group 4 metal carboranyl complexes was achieved by reactions of [eta5:sigma-Me2C(C5H 4)(C2B10H10]M[NMe2) 2 (M = Zr, Hf), [eta5:sigma-Me2C(C 9H6)(C2B10H10]Zr[NMe 2)2 or [eta5:sigma-H2C(C 13H8)(C2B10H10]Zr[NMe 2)2 with excess diamines. The resultant metal dicarbollide complexes [eta5:eta6-Me2C(C 5H4)(C2B9H10)]Zr[eta 2-N(Me)(Ch2)2NH(Me)] and [eta5:eta 6-Me2C(C5H4)(C2B 9H10]Zr[eta2-[NMe)(CH2) 3NH(Me)] were active toward unsaturated molecules, like nBuNCS, iPr-N=C=N- iPr and nBuNC, to give mono-insertion products. [eta5:eta6-Me2C(C 5H4)(C2B9H10)]Zr[eta 2-N(Me)(CH2)3NH(Me)] was able to be deprotonated by nBuLi to give a lithium salt {[eta 5:eta-6-Me2C(C5H4)(C 2B9H10)]Zr[eta2-N(Me)(CH 2)3N(Me)Li]}2. It reacted with [HNEt3][BPh 4] to afford cationic zirconium species [eta5:eta 6-Me2C(C5H4)(C2B 9H10]Zr{eta2-NH(Me)(CH2) 3NH(ME)}][BPh4]. The dichloro species [eta5:eta 6-Me2C(C5H4)(C2B 9H10}MCl2][Li(DME)3)] (M = Zr, Hf) were reduced by sodium metal to produce a new class of metallacarbornes bearing arachno-eta6-C2B9 tetraanion. / The amine exchange reaction between [eta5:sigma-Me 2C(C5H4)(C2B10H10]M[NMe 2)2 (M = Zr, Hf, Ti) and N, N'-dimethylethylenediamine or N, N'-dimethylpropane-1,3-diamine gave [eta5:sigma-Me 2C(C5H4)(C2B10H10]M-[eta 2N(Me)(CH2)2N(Me)] (M = Zr, Ti) or [eta 5:sigma-Me2C(C5H4)(C2B 10H10]M-[eta2N(Me)(CH2) 3N(Me)] (M= Zr, Hf, Ti) in good yields. The metal-nitrogen bonds in these group 4 metal diamide complexes were very reactive toward unsaturated polar organic substrates, such as RNC, RNCS, RNCO, R-N=C=N-R and RCN to give multiple insertion products. The carbodiimide and XylNC (Xyl = 2,6-Me 2C6H3) insertion products [eta5:sigma-Me 2C(C5H4)(C2B10H10]M-[eta 3N(Me)(CH2)3N(Me)C(=NR)NR] (M = Zr, R = iPr, Cy; M = Hf, R = Cy) and [eta5:sigma-Me 2C(C5H4)(C2B10H10]M-[eta 2:eta2-N(Xyl)=CN(Me)(CH2)3N(Me)C=N(Xyl)] (M = Zr, Hf) also showed reactivities toward unsaturated molecules, resulting in the de-insertion of carbodiimide and XylNC. Different reactivity patterns were observed, depending on the nature of metal atoms and substrates. / Sit, Mei Mei. / Adviser: Zuowei Xia. / Includes supplementary digital materials. / Source: Dissertation Abstracts International, Volume: 73-01, Section: B, page: . / Thesis (Ph.D.)--Chinese University of Hong Kong, 2010. / Includes bibliographical references (leaves 247-267). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Electronic reproduction. [Ann Arbor, MI] : ProQuest Information and Learning, [201-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstract also in Chinese.

Yeung, Lai Fong. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2010. / Includes bibliographical references (leaves 122-124). / Abstracts in English and Chinese. / Abstract --- p.i / 摘要 --- p.iii / Acknowledgement Contents --- p.iv / Abbreviations --- p.ix / List of Compounds --- p.xi / Chapter Chapter One - --- Introduction / Chapter 1.1 --- General Background of Amido Ligands --- p.1 / Chapter 1.2 --- General Background of Guanidinates --- p.2 / Chapter 1.3 --- Coordination modes of Guanidinate Ligands --- p.5 / Chapter 1.4 --- A Brief Review on the Coordination Chemistry of Guanidinate Complexes --- p.7 / Chapter 1.4.1 --- Main Group Metal Guanidinate Complexes --- p.7 / Chapter 1.4.2 --- Transition Metal Guanidinate Complexes --- p.12 / Chapter 1.4.3 --- Rare Earth Metal Guanidinate Complexes --- p.13 / Chapter 1.5 --- Preparations of Metal Guanidinate Complexes --- p.15 / Chapter 1.6 --- Applications of Guanidinate Complexes --- p.16 / Chapter 1.7 --- Objectives of This Work --- p.18 / Chapter 1.8 --- References for Chapter One --- p.19 / Chapter Chapter Two - --- Synthesis and Structural Characterization of Bis(guanidinate) Complexes / Chapter 2.1 --- Introduction to Guanidinate Complexes --- p.25 / Chapter 2.1.1 --- Guanidinate Complexes of the Alkali Metals --- p.25 / Chapter 2.1.2 --- Bis(guanidinate) Complexes of Divalent First-Row Late Transition Metals --- p.27 / Chapter 2.1.3 --- Bis(guanidinate) Complexes of Group 12 Metals --- p.28 / Chapter 2.2 --- Objectives of Our Study --- p.29 / Chapter 2.3 --- Results and Discussion --- p.30 / Chapter 2.3.1 --- Synthesis and Structures of Lithium Guanidinates --- p.30 / Chapter 2.3.1.1.1 --- Synthesis of (L1 = [(C6H3Me2-2J6)NC{N(H)Cy}NCy] (1); L2=[(C6H3Me2-2)6)NC{N(H)Pr/}NPrl (2) and L3 =[(C6H3Me2_2，6)NC{N(SiMe3)Cy}NCy] (5)) --- p.30 / Chapter 2.3.1.1.2 --- Physical Characterization of Compounds 1，2 and 5 --- p.31 / Chapter 2.3.1.1.3 --- Molecular Structures of Compounds 1，2 and 5 --- p.32 / Chapter 2.3.1.2.1 --- Synthesis of Solvated Lithium Guanidinate [Li(L1)(THF)]2(6) --- p.37 / Chapter 2.3.1.2.2 --- Physical Characterization of Compound 6 --- p.37 / Chapter 2.3.1.2.3 --- Molecular Structure of Compound 6 --- p.38 / Chapter 2.3.2 --- Synthesis and Structures of Manganese(ll) Bis(guanidinate) Complexes --- p.40 / Chapter 2.3.2.1 --- Synthesis of Manganese(ll) Bis(guanidinate) Complexes Supported by Ln (n = 1-3) --- p.40 / Chapter 2.3.2.2 --- Physical Characterization of Compounds 7-9 --- p.41 / Chapter 2.3.2.3 --- Molecular Structures of Compounds 7-9 --- p.42 / Chapter 2.3.3 --- Synthesis and Structures of Iron(ll) Bis(guanidinate) Complexes --- p.51 / Chapter 2.3.3.1 --- Synthesis of Iron(ll) Bis(guanidinate) Complexes Supported by Ln (n = 2，3) --- p.51 / Chapter 2.3.3.2 --- Physical Characterization of Compounds 10 and 11 --- p.52 / Chapter 2.3.3.3 --- Molecular Structures of Compounds 10 and 11 --- p.52 / Chapter 2.3.4 --- Synthesis and Structures of Cobalt(ll) Bis(guanidinate) Complexes --- p.57 / Chapter 2.3.4.1 --- Synthesis of Bis(guanidinate) Cobalt(ll) Complexes Supported by Ln (n = 1-3) --- p.57 / Chapter 2.3.4.2 --- Physical Characterization of Compounds 12-14 --- p.57 / Chapter 2.3.4.3 --- Molecular Structures of Compounds 12-14 --- p.58 / Chapter 2.3.5 --- Synthesis and Structures of Nickel(II) Bis(guanidinate) Complexes --- p.65 / Chapter 2.3.5.1 --- "Synthesis of Nickel(ll) Bis(guanidinate) Complexes Supported by Ln (n = 1, 2)" --- p.65 / Chapter 2.3.5.2 --- Physical Characterization of Compounds 15 and 16 --- p.66 / Chapter 2.3.5.3 --- Molecular Structures of Compounds 15 and 16 --- p.66 / Chapter 2.3.6 --- "Synthesis and Structures of Bis(guanidinate) Complexes of Group 12 Metal (M = Zn, Cd)" --- p.71 / Chapter 2.3.6.1 --- Synthesis of Zn(ll) and Cd(ll) Bis(guanidinate) Complexes Supported by Ln (n = 1-3) --- p.71 / Chapter 2.3.6.2 --- Physical Characterization of Compounds 17-20 --- p.72 / Chapter 2.3.6.3 --- Molecular Structures of Compounds 17-20 --- p.72 / Chapter 2.4 --- Summary for Chapter Two --- p.82 / Chapter 2.5 --- Experimental for Chapter Two --- p.83 / Chapter 2.6 --- References for Chapter Two --- p.92 / Chapter Chapter Three - --- "Synthesis and Structural Characterization of Mono(guanidinate) Complexes of Mn(ll), Fe(ll) and Cu(l)" / Chapter 3.1 --- Introduction --- p.95 / Chapter 3.1.1 --- Introduction of Mono(guanidinate) Complexes of the First-Row Divalent Late Transition Metals --- p.95 / Chapter 3.1.2 --- Alkyl Complexes of the Late Transition Metals --- p.99 / Chapter 3.1.3 --- Introduction of Mono(guanidinate) Complexes of Cu(l) --- p.101 / Chapter 3.2 --- Objectives of Our Study --- p.102 / Chapter 3.3 --- Results and Discussion --- p.103 / Chapter 3.3.1 --- Synthesis and Structures of Mono(guanidinate) Complexes Supported by L3 --- p.103 / Chapter 3.3.1.1 --- Synthesis of Mono(guanidinate) Metal (M = Mn 21， Fe 22) Complexes Supported by L3 --- p.103 / Chapter 3.3.1.2 --- Physical Characterization of Compounds 21 and 22 --- p.103 / Chapter 3.3.1.3 --- Molecular Structures of Compounds 21 and 22 --- p.104 / Chapter 3.3.2 --- "Synthesis and Structures of Monoalkyl Metal (M = Mn, Fe) Complexes Supported by the Guanidinate Ligand L3" --- p.110 / Chapter 3.3.2.1 --- "Synthesis of Monoalkyl Metal (M = Mn, Fe) Complexes Supported by the Guanidinate Ligand L3" --- p.110 / Chapter 3.3.2.2 --- Physical Characterization of Compound 23 --- p.111 / Chapter 3.3.2.3 --- Molecular Structure of Compound 23 --- p.111 / Chapter 3.3.3 --- Synthesis and Structure of a Copper(l) Guanidinate Complex Supported by L2 --- p.115 / Chapter 3.3.3.1 --- Synthesis of a Copper(l) Guanidinate Complex Supported by L2 --- p.115 / Chapter 3.3.3.2 --- Physical Characterization of Compound 24 --- p.115 / Chapter 3.3.3.3 --- Molecular Structure of Compound 24 --- p.116 / Chapter 3.4 --- Summary for Chapter Three --- p.119 / Chapter 3.5 --- Experimental for Chapter Three --- p.119 / Chapter 3.6 --- References for Chapter Three --- p.122 / "Appendix 1 - Physical Measurements, X-Ray Structural Analysis" --- p.125 / Appendix 2 - NMR Spectra of Compounds --- p.127 / Appendix 3 - Selected Crystallographic Data --- p.139

Cheng, Yat Ho. / Thesis submitted in: October 2007. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2008. / Includes bibliographical references. / Abstracts in English and Chinese. / Abstract --- p.i / 摘要 --- p.iii / Acknowledgment --- p.iv / Contents --- p.v / Abbreviations --- p.xi / Chapter Chapter I. --- Model Studies for Catechol Dioxygenases / Chapter I.1 --- General Background / Chapter I.2 --- Intradiol-Cleaving Catechol Dioxygenases --- p.2-4 / Chapter I.3 --- Extradiol-Cleaving Catechol Dioxygenases --- p.5-8 / Chapter I.4 --- Selectivity of Intra- versus Extradiol-Cleaving Pathways --- p.8-10 / Chapter I.5 --- Early Studies on Model Complexes for Catechol Dioxygenases --- p.10-16 / Chapter I.6 --- Spin Crossover Study of Model Complexes --- p.16-18 / Chapter I.7 --- Model complexes for the Extradiol-Cleaving Dioxygenases --- p.19-23 / Chapter I.8 --- Objectives of this Work --- p.23 / Chapter I.9 --- References for Chapter I --- p.24-31 / Chapter Chapter II. --- "Synthesis and Reactivity Studies of Model Complexes of Catechol Dioxygenases Supported by the anionic Hydrotris-3,5-dimethylpyrazolylborate Ligand" / Chapter II.1 --- Introduction --- p.32-33 / Chapter II.2 --- Result and Discussion --- p.34-60 / Chapter II.2.1 --- Synthesis of Iron(III) Catecholate Complexes --- p.34-37 / Chapter II.2.2 --- Molecular Structures --- p.38-45 / Chapter II.2.3 --- Electrochemical Studies --- p.46-48 / Chapter II.2.4 --- UV-Vis Spectroscopic Studies --- p.49-55 / Chapter II.2.4.1 --- Oxygenation Studies of the Catecholate Complexes --- p.49-51 / Chapter II.2.4.2 --- Spectral Studies at low Temperature --- p.52-54 / Chapter II.2.4.3 --- Reactivity Studies with Excess Pyrazole --- p.54-55 / Chapter II.2.5 --- Identification of the degradation products --- p.56-60 / Chapter II.3 --- Summary --- p.61 / Chapter II.4 --- Experiments for Chapter II --- p.62-66 / Chapter II.4.1 --- Materials --- p.62 / Chapter II.4.2 --- Synthesis of complexes --- p.62-64 / Chapter II.4.3 --- Characterization of degradation products --- p.65-66 / Chapter II.5 --- References for Chapter II --- p.67-70 / Chapter Chapter III. --- "Synthesis and Reactivity Studies of Model Complexes of Catechol Dioxygenases Supported by the neutral Hydrotris-3,5-dimethylpyrazolylmethane Ligand" / Chapter III.1 --- Introduction --- p.71-72 / Chapter III.2 --- Results and Discussion --- p.73-96 / Chapter III.2.1 --- Synthesis --- p.73-78 / Chapter III.2.1.1 --- Synthesis of Iron(III)-Catecholate Complexes --- p.73-74 / Chapter III.2.2.2 --- Attempt to Synthesis Iron(III)-Catecholate Complexes with Pyrocatechol --- p.75-76 / Chapter III.2.2.3 --- Attempts to Remove the Chloride Ligand from the Iron(III) Catecholate Complexes --- p.76-77 / Chapter III.2.2.4 --- Synthesis of Iron(II)-Catecholate Complexes --- p.77-78 / Chapter III.2.2 --- Molecular Structures --- p.79-85 / Chapter III.2.3 --- Electrochemical Studies --- p.86-88 / Chapter III.2.4 --- UV-Vis Spectroscopic and Reactivity Studies on Oxygenation of / Chapter III.2.4.1 --- Oxygenation Studies of the Catecholate Complexes --- p.89-90 / Chapter III.2.4.2 --- Spectral changes with chloride removed from the catecholate complex --- p.91-93 / Chapter III.2.5 --- Identification of the degradation products --- p.94-96 / Chapter III.3 --- Summary --- p.96 / Chapter III.4 --- Experimental for Chapter III --- p.97-101 / Chapter III.4.1 --- Materials --- p.97 / Chapter III.4.2 --- Synthesis of complexes --- p.97-99 / Chapter III.4.3 --- Characterization of Oxygenation Products --- p.100 / Chapter III.5 --- References for Chapter III --- p.101-105 / Chapter Chapter IV. --- "Synthesis and Reactivity Studies of Manganese and Cobalt Catecholate Complexes Supported by the anionic Hydrotris-3,5-dimethyl -pyrazolylborate Ligand" / Chapter IV.1 --- Introduction --- p.106-109 / Chapter IV.2 --- Results and Discussion --- p.110-127 / Chapter IV.2.1 --- Synthesis of Manganese and Cobalt Catecholate Complexes --- p.110-111 / Chapter IV.2.2 --- Molecular Structures --- p.112-118 / Chapter IV.2.3 --- UV-Vis Spectroscopic Studies and Reactivity Studies --- p.119-124 / Chapter IV.2.3.1 --- Oxygenation studies of the Manganese(III)-Catecholate Complex --- p.119-121 / Chapter IV.2.3.1 --- Oxygenation studies of the Cobalt(II)-catecholate Comple --- p.x / Chapter IV.2.4 --- Identification of Degradation Products --- p.124-126 / Chapter IV.3 --- Summary --- p.126 / Chapter IV.4 --- Experimental for Chapter IV --- p.127-129 / Chapter IV.4.1 --- Materials --- p.127 / Chapter IV.4.2 --- Synthesis of complexes --- p.127-129 / Chapter IV.5 --- References for Chapter IV --- p.130-135 / Appendix I / Chapter A.I.1 --- General Procedure --- p.136 / Chapter A.I.2 --- Physical Characterization --- p.136-138 / Appendix II / Chapter A.II.1 --- "Selected Crystallographic Data for Compounds 1，2，4,5，7，9，14，15，16，17 and 18" --- p.142-147 / Chapter A.II.2 --- 1H and 13C NMR Spectra --- p.148-150 / Chapter A.II.3 --- Chromatogram and Mass spectra (El and Cl) from GCMS Analysis --- p.151-157 / Chapter A.II.4 --- Mass Spectra --- p.158-162

Intramolecular non-covalent interactions between aromatic ligands in chiral Ru(II) and Co(III) complexes have been investigated in this study. Several investigations were carried out and findings given. The results of the study, which demonstrate the significance of non-covalent interactions involving aromatic residues to the determination of the molecular conformation, serve to highlight the suitability of simple chiral metal complexes to act as models for interactions / Doctor of Philosophy (PhD)

The reaction of Mg(NPh2)2 with LiNR2 (R= SiMe3, NiPr, NiBu) generated the same product, [Mg(NPh2)3(THF)][Li(THF)4] which was identified by 1H-NMR and X-ray crystallography. The magnesium-lithium mixed metal complex reacted with excess carbon dioxide in the ice bath to generate the tetralithium complex, Li4(O2CNPh2)4(THF)4 which was identified by 1H-NMR, 13C-NMR, IR, and X-ray crystallography.