pt I. Heterobimetallic complexes of PPh2, trans-(CO)3Fe(Ph2Ppy)2 and trans-(CO)3Fe(Ph2Ppym)2 -- pt II. Metal complexes of tertiary phosphine betaines. / by Song-Lin Li. / Thesis (Ph.D.)--Chinese University of Hong Kong, 1996. / Includes bibliographical references (leaves 77-83, 167-173). / Acknowledgments / Abstract --- p.i-ii / Table of Contents --- p.iii-iv / Structural Formulas of Ligands --- p.v / Index of Compounds --- p.vi-vii / List of Tables --- p.viii-ix / List of Figures --- p.x-xii / Chapter Part I. --- " HeterobimetaUic Complexes of PPh2-, trans- (CO)3Fe(Pli2Ppy)2 and trans-(CO)3Fe(Ph2Ppym)2" --- p.1 - 83 / Chapter 1. --- Introduction --- p.1-11 / Chapter 2. --- Results and Discussion / Chapter 1. --- "Synthetic and Structural Characterization of the Phosphido-Bridgcd Heterobimetallic Transition Metal Complex, (OC)3Fe(μ-PPh2)2Mo(CO)4" --- p.12-18 / Chapter 2. --- ############################################################################################################################################################################################################################################################### --- p.19-36 / Chapter 3. --- Coordination Chemistry of a New Neutral Organomctallic Tridcntate Ligand trans-(CO)3Fe(Ph2Ppym)2 (Ph2Ppym = 2-(di --- p.37-76 / Chapter 1. --- Synthesis and Crystal Structure of trans-(CO)3Fe(Ph2Ppym)2 --- p.38-42 / Chapter 2. --- "Mono-, Di- and Tridcntate Coordination Modes of trans-(CO)3Fe(Ph2Ppym)2 Towards Mercury(II) Halide/Pscudohalide" --- p.42-52 / Chapter 3. --- "Synthesis and Crystal Structures of Complexes Containing an Fe→Cd Donor-Acceptor Bond Formed by Reaction of trans-(CO)3Fe(Ph2Ppym)2 with CdX2 (X = C1, Br, I，SCN, C1O4)" --- p.53-65 / Chapter 4. --- "Miscellaneous: Interaction of trans-(CO)3Fe (Ph2Ppym)2 with Hg2(ClO4)2.xH2O，[(cod)RhCl]2, (cod)PdCl2, PdCl2 and Nd(SCN)3 .xH2O" --- p.66-76 / References --- p.77-83 / Chapter Part II. --- Metal Complexes of Tertiary Phosphine Betaines --- p.84-173 / Chapter 3. --- Introduction --- p.84-96 / Chapter 4. --- Results and Discussion / Chapter 1. --- Betaine Derivatives --- p.97-109 / Chapter 2. --- Cadmium(II) Complexes with Tertiary Phosphine Bctaincs --- p.110-145 / Chapter 1. --- """Paddle wheel-like"" cadmium(II) complexes" --- p.111-116 / Chapter 2. --- "Discrete Mono-, Bi-, Tri- and Tctra-nuclcar Complexes of Cadmium(II) with Ph3P+(CH2)2CO2-" --- p.116-129 / Chapter 3. --- A Layer-Type Complex of Cadmium(II) Chloride/Pcrchlorate with Triphenylphosphoniopropionate (Ph3P+(CH2)2C02 -) --- p.130-133 / Chapter 4. --- A Layer-Type Complex of Cadmium(II) Chloride/Pcrchlorate with Triphenylphosphoniopropionate (Ph3P+(CH2)2C02-) --- p.134-139 / Chapter 5. --- Mixed-ligand Cadmium(II) Complexes of Ph3P(CH2)2CO2- and Me2N(CH2)2NMe2 (tmen) --- p.139-144 / Chapter 3. --- Zinc(II) and Mercury(II) Complexes --- p.146-155 / Chapter 1. --- Synthesis and Structural Characterization of Mono- and Dinuclcar Zinc(II) Complexes of Triphenylphosphoniopropionate --- p.146-151 / Chapter 2. --- Interaction of Mercury(II) Halidcs with Tertiary Phosphine Bctaines --- p.151-155 / Chapter 4. --- "Cobalt(II), Copper(II) and Silver(I) Complexes" --- p.156-166 / References --- p.167-173 / Chapter 5. --- Conclusion --- p.174-178 / Chapter 6. --- Experimental --- p.179-203 / Appendix A Table of Atomic Coordinates and Thermal Parameters --- p.204-226 / Publications based on results reported in this thesis --- p.227-228

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

No description available.

Shaowu Wang. / "August 1999." / Thesis (Ph.D.)--Chinese University of Hong Kong, 1999. / Includes bibliographical references (p. 125-143). / 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.

In Chapter One, the sodium salt of tris (2-oxo-1-t-butylimidazolyl) hydroborate, [To^But]Na, as an [O_3] donor ligand has been prepared. The yield for this reaction was low because there is a significant amount of side product in which the double bond of the oxoimidazole starting material is reduced. Treatment of sodium borohydride with bezannulated oxoimidazole at high temperature leads to the generation of the sodium salt of tris (2-oxo-1-R-methylbenimidazolyl) hydroborate in high yield, [To^RBenz]Na. These ligands have been prepared with different alkyl substituents, methyl, t-butyl and adamantyl, to achieve the desired steric environment. Furthermore, these benzannulated ligand have been used to synthesize a series [To^RBenz]Tl complexes, which exist as a discrete mononuclear complexes in the solid state. Finally, [To^RBenz]Tl complexes are more pyramidal than the sulfur counterpart, [Tm^RBenz]Tl, but less pyramidal than those in the tris (pyrazolyl)hydroborato counterpart, [Tp^R,R]]Tl. In Chapter Two, the properties of [To^R] ligands have been evaluated versus related L_2X ligands. [To^R] ligands are substantially more sterically demanding than the corresponding [Tm^R] sulfur donor ligand and related [O_3] donor ligands. However, electronically, the [To^R] ligands exhibit weaker electron donating properties than other L_2X type ligands. Finally, the coordination chemistry of [To^R] ligands with various metal compounds has been briefly investigated. The synthesis of a new class of bidentate ligands has been detailed in Chapter Three. Namely the bis(2-oxo-1-t-butylimidazolyl)hydroborato and bis (2-oxo-1-alkylbenzimidazolyl)hydroborato, [Bo^But] and [Bo^RBenz], have been synthesized via the reaction of MBH_4 with two equivalents of the respective 2-imidazolone. Chelation of [Bo^But] and [Bo^MeBenz] to a metal center results in a flexible 8-membered ring that is capable of adopting a "boat-like" conformation that allows for secondary M—H—B interactions. Chapter Four describes the synthesis of [Bo^RBenz]_2Zr(CH_2Ph)_2and [To^RBenz]Zr(CH_2Ph)_3 with different alkyl substituents. Treatment of [To^ButBenz]Zr(CH_2Ph)_3 with ([PhNHMe_2][B{C_6F_5}_4]) in a coordinating solvent, Et_2O, generates {[To^ButBenz]Zr(CH2Ph)_2(OEt_2)}{B(C_6F_5)_4} which exhibit a very low activity for ethylene polymerization. However, a coordinatively unsaturated cationic zirconium alkyl complex was obtained by the treatment of ([PhNHMe_2][B{C_6F_5}_4]) with [To^ButBenz]Zr(CH_2Ph)_3 or [To^AdBenz]Zr(CH_2Ph)_3 which generate [To^ButBenz]Zr(CH_2Ph)_2[B(C_6F_5)_4 or [To^AdBenz]Zr(CH_2Ph)_2[B(C_6F_5)_4], respectively. Moderate activity for ethylene polymerization was obtained for t-butyl while high activity was obtained for the adamantyl derivatives. Finally, Chapter Five describes the synthesis of new oxygen-rich ligands, namely tris (2-pyridonyl)methane, [Tpom^R]H. They are obtained via the reaction of 2-pyridones with CHX_3 and K_2CO_3 in the presence of [Bu^n _4N]Br, followed by acid-catalyzed isomerization with camphorsulfonic acid. These compounds provide access to a new class of L_3X alkyl ligands that feature oxygen donors and are capable of forming metallacarbatranes, as exemplified by [Κ^4-Tpom^But]ZnOC6H4Bu^t. In addition, the [Tpom^But] ligand also allows isolation of a monovalent thallium alkyl compound, [Tpom^But]Tl, in which the Tl—C bond is long and has little covalent character.

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.

Yu Michael. / Thesis submitted in: July 2003. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2004. / Includes bibliographical references (leaves 57-63). / Abstracts in English and Chinese. / Table of Contents --- p.i / Acknowledgments --- p.iii / Abbreviations --- p.iv / Abstract --- p.v / Chapter Part I - --- Optimization of Palladium Catalyzed Phosphination / Chapter Chapter 1 --- General Introduction / Chapter 1.1 --- Background of Phosphine Synthesis --- p.1 / Chapter 1.2 --- Preparation of Phosphines --- p.4 / Chapter Chapter 2 --- Optimization of Phosphination of Aryl Bromides / Chapter 2.1 --- Additive Effect in Phosphination of Aryl Bromides --- p.14 / Chapter 2.2 --- Iodide Effect in Phosphination of Aryl Triflate --- p.25 / Chapter 2.3 --- Low Temperature Phosphination --- p.27 / Chapter 2.4 --- Conclusion --- p.29 / Chapter Part II - --- Synthesis of Optically Active As，N Ligands and Their Metal Complexes / Chapter Chapter 1 --- 3.1 Introduction --- p.30 / Chapter Chapter 2 --- Synthesis of Optically Active As，N Ligands and Their Metal Complexes / Chapter 4.1 --- "Synthesis of As,N Oxazolines" --- p.39 / Chapter 4.2 --- "Synthesis of As,N Oxazoline Transition Metal Complexes" --- p.41 / Chapter 4.3 --- Conclusion --- p.44 / Experimental --- p.45 / References --- p.57 / Appendix --- p.64

[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.

A new class of ruthenium-COD complexes containing carbon-bridged carboranyl-cyclopentadienyl (-indenyl or -fluorenyl) ligands was synthesized. These complexes showed a different reactivity in COD displacement reactions in comparison with the classical LRuCl(COD) (L = Cp, indenyl) complexes presumably due to the presence of sterically bulky and constrained organic-inorganic hybrid ligands. However, the COD ligands in these complexes can be replaced by bidentate tertiary phosphines, 2,2'-bipyridine, mono-phosphites with small cone angles, primary amines or N-heterocyclic carbene to give the corresponding COD displacement complexes. The ruthenium-amine complexes are much more labile than the ruthenium-COD ones. The amine ligands can be substituted by CH3CN to afford more active ruthenium-acetonitrile complex. / Reactions of dilithium salt of linked cyclopentadienyl-carboranyl ligands with 1 equiv of RuCl2(PPh3)3 in THF afforded the corresponding doubly-linked cyclopentadienyl-carboranyl ruthenium(II) hydride complexes. Such intramolecular coupling of a cyclopentadienyl with an o-carboranyl unit is driven by steric factors. Both carboranyl and phosphines with large cone angles are essential for such coupling reactions. The doubly-linked cyclopentadienyl-carboranyl compound was released from the corresponding ruthenium hydride complex by treatment with excess HBF 4·OEt2, followed by hydrolysis. This ligand is not accessible by any other known methods. / Reactions of the ruthenium-acetonitrile complex with SiMe3 substituted alkynes afforded mononuclear bis(vinylidene)metal or vinylvinylidenemetal, respectively, indicating that sterically demanding ancillary ligand and bulky alkynes are both important components to stabilize the above complexes. Treatment of the ruthenium-acetonitrile complex with internal alkynes afforded eta 4-Ru cyclobutadiene or ruthenacyclopentatriene complexes, respectively. Interestingly, interaction of ruthenium-acetonitrile complex with terminal aromatic alkynes gave ruthenium tricyclic complexes involving coupling reactions between Cp and alkynes. The possible reaction mechanism was proposed with the help of the DFT calculations. / Reactions of the ruthenium-amine complex with alkynes gave ruthenium aminocarbene or enamine complexes depending on the electronic properties of alkynes. Electron-rich alkynes gave aminocarbene complexes, whereas electron-deficient alkynes afforded enamine ones. The [eta5:sigma-Me 2C(C5H4)(C2B10H10)]Ru fragment remained intact during the reactions, which may play a role in these controlled reactions. / Sun Yi. / "May 2006." / Adviser: Zuowei Xie. / Source: Dissertation Abstracts International, Volume: 67-11, Section: B, page: 6398. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2006. / Includes bibliographical references (p. 157-177). / 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, [200-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstracts in English and Chinese. / School code: 1307.

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