Complexes of the type MX(η²-NO₃)(CO)₂(PPh₃)₂, (M = Mo, X = Cl, Br; M = W, X = Br) were prepared from the reactions of MX₂(CO)₂(PPh₃)₂ with ammonium nitrate in acetone. The complexes were characterized by elemental analyses, ¹⁵N labelling, infrared and NMR spectroscopy. The nitrate ligand is bidentate and the complexes are seven-coordinate. Novel nitrite complexes of molybdenum and tungsten of the type M(NO₂)₂(PPh₃)₂ were prepared. The compounds were characterized by elemental analyses, ¹⁵N labelling, infrared and multinuclear NMR spectroscopy. Both NO₂ ligands are chelating and the two NO₂, PPh₃ and CO ligands are equivalent. Molybdenum dinitrosyl complexes were synthesized by the reduction of nitrate ions. The crystal structure of cis-dinitrosyl-cis-dichloro-trans-bis-(triphenylphosphine)molybdenum(II) was determined by x-ray diffraction. Both the nitrosyl groups are linear. Mo(NO)₂Cl₂(OPPh₃)₂ and Mo(NO)₂Cl(NO₃)(OPPh₃)₂ were synthesized by the reaction of MoCl(η²-NO₃)(CO)₂(PPh₃)₂ with NO in acetone/toluene mixture. The nitrosyl ligands are linear and the phosphineoxide ligands are cis to each other. The dinitrite complex Rh(NO)(NO₂)₂(PPh₃)₂ of the series Rh(NO)X₂(PPh₃)₂ (X - monodentate anions) was prepared as a direct derivative of Rh(NO)Cl₂(PPh₃)₂ by its reaction with sodium nitrite. The complex is square pyramidal with an apical nitrosyl ligand. The two NO₂ groups are present as the nitro and the nitrito group. Rh(NO)(NO₂)₂(PPh₃) reacted with oxygen and formed Rh(NO₃)₃(PPh₃)₂. The reaction of Rh(NO)(NO₂)₂(PPh₃)₂ with CO in acetonitrile produced Rh(CO)(NO₂)(PPh₃)₂. The complex Rh(CO)(NO₂)(PPh₃)₂ is square planar with the phosphine ligands in the trans positions.

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Chung Hei Lam. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2001. / Includes bibliographical references. / Abstracts in English and Chinese. / Table of Contents --- p.i / Acknowledgements --- p.iv / Abstracts --- p.v / 摘要 --- p.vii / List of Compounds --- p.ix / List of Tables --- p.xii / List of Figures --- p.xiv / Abbreviations --- p.xv / Chapter CHAPTER 1. --- SYNTHESIS OF LATE TRANSITION METAL AMIDES / Chapter 1.1 --- GENERAL BACKGROUND --- p.1 / Chapter 1.2 --- PREPARATIONS OF LATE TRANSITION METAL AMIDES --- p.2 / Chapter 1.3 --- OBJECTIVES OF THIS WORK --- p.3 / Chapter 1.4 --- REFERENCES FOR CHAPTER1 --- p.5 / Chapter CHAPTER 2. --- "SYNTHESIS, STRUCTURES AND REACTIVITIES OF IRON(II) AND COBALT(II) AMIDES" / Chapter 2.1 --- INTRODUCTION --- p.7 / Chapter 2.1.1 --- A General Review on Iron(II) and Cobalt (II) Amides --- p.7 / Chapter 2.1.2 --- A General Review on Iron(II) and Cobalt(II) Thiolates --- p.9 / Chapter 2.1.3 --- A General Review on Iron(II) and Cobalt(II) Alkoxides and Aryloxides --- p.11 / Chapter 2.2 --- RESULTS AND DISCUSSION --- p.13 / Chapter 2.2.1 --- Synthesis of the Ligand Precursor LH (1) and the Corresponding Lithium Reagents [Li(L)(TMEDA)] (2) and LiL (3) --- p.13 / Chapter 2.2.2 --- Synthesis´ة Structures and Reactivities of Mononuclear Iron(II) and Cobalt(II) Amides --- p.14 / Chapter 2.2.2.1 --- Synthesis of Mononuclear Iron(II) and Cobalt(II) Amides --- p.14 / Chapter 2.2.2.2 --- Reactions of Compound 4 with ArMe OH and ArSH --- p.18 / Chapter 2.2.2.3 --- Physical Characterization of Compounds 4-6 --- p.19 / Chapter 2.2.2.4 --- Molecular Structures of Compounds 4-6 --- p.20 / Chapter 2.2.3 --- "Synthesis, Structures and Reactivities of Binuclear Iron(II) and Cobalt (II) Amides" --- p.31 / Chapter 2.2.3.1 --- Synthesis of Binuclear Iron(II) and Cobalt(II) Amides --- p.31 / Chapter 2.2.3.2 --- Reactions of Compounds 7 and 8 with Protic Reagents --- p.33 / Chapter 2.2.3.3 --- "Attempted Reactions of Compounds 7 and 8 with 3,5-di-tert- butylcatechol" --- p.35 / Chapter 2.2.3.4 --- Physical Characterization of Compounds 7-14 --- p.35 / Chapter 2.2.3.5 --- Molecular Structures of Compounds 7-10 and 13-14 --- p.38 / Chapter 2.3 --- EXPERIMENTALS FOR CHAPTER 2 --- p.57 / Chapter 2.4 --- REFERENCES FOR CHAPTER 2 --- p.64 / Chapter CHAPTER 3. --- SYNTHESIS AND STRUCTURES OF MANGANESE(II) AMIDES / Chapter 3.1 --- INTRODUCTION --- p.68 / Chapter 3.2 --- RESULTS AND DISCUSSION --- p.70 / Chapter 3.2.1 --- Synthesis of Manganese(II) Amide --- p.70 / Chapter 3.2.2 --- Physical Characterization of Compound 15 --- p.72 / Chapter 3.2.3 --- Molecular Structure of Compound 15 --- p.73 / Chapter 3.3 --- EXPERIMENTALS FOR CHAPTER 3 --- p.78 / Chapter 3.4 --- REFERENCES FOR CHAPTER 3 --- p.79 / "APPENDIX 1 General Procedures, Physical Measurements and X-ray Structure Analysis" --- p.81 / APPENDIX 2 Table A-1. Selected crystallographic data for compounds 4-6. --- p.84 / Table A-2. Selected crystallographic data for compounds 7-10. --- p.85 / Table A-3. Selected crystallographic data for compounds 13-15 --- p.86

Suk-Yu Wong. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2002. / Includes bibliographical references. / Abstracts in English and Chinese. / Acknowledgements --- p.i / Abstract --- p.ii / 中文摘要 --- p.iv / List of Compounds Synthesized --- p.vi / List of Abbreviation --- p.viii / Contents --- p.x / Chapter CHAPTER 1 --- Development of Phosphoranoimine as a Ligand for the Synthesis of Metal Complexes / Chapter 1.1 --- Introduction / Chapter 1.1.1 --- General Aspects of Phosphoranoimine --- p.1 / Chapter 1.1.2 --- General Aspects of Transition Metal Phosphoranoimine Complexes --- p.3 / Chapter 1.1.3 --- Reaction with Organolithium Compounds --- p.6 / Chapter 1.1.5 --- Objective of this Work --- p.8 / Chapter 1.2 --- Results and Discussion / Chapter 1.2.1 --- Synthesis and Characterization of Phosphoranoimine Ligand (9a and 9b) --- p.11 / Chapter 1.2.2 --- Synthesis of Dilithium Phosphoranoimine Complex (10a) --- p.14 / Chapter 1.2.3 --- Synthesis of Monolithium Phosphoranoimine Complex (10b) --- p.16 / Chapter 1.2.4 --- "Molecular Structures of Dilithium Complex and Monolithium Complex [Li2{2，6-(Me3SiN=PPh2CH)2C5H3N}THF] (10a) and [Li{2,6-(Me3SiN=PPri2CH)(Me3SiN=PPri2CH2)C5H3N}] (10b)" --- p.17 / Chapter 1.3 --- Experimental Section --- p.21 / Chapter 1.4 --- References --- p.27 / Chapter CHAPTER 2 --- Synthesis and Characterization of Transition Metal Complexes Containing Phosphoranoimine Ligands / Chapter 2.1 --- Introduction --- p.30 / Chapter 2.2 --- Results and Discussion / Chapter 2.2.1 --- "Synthesis and Characterization of Titanium(IV) Phosphoranoimido Complexes [Ti{N=(2-CH2Py)PPr i2 }C13(THF)] (11) and [Ti2{ {N=PPh2CH2}2 C5H3N-2,6}{(μ-Cl)2Cl4(THF)2}]n (12)" --- p.33 / Chapter 2.2.2 --- "Molecular Structures of [Ti{N=(2-CH2Py)PPri2}Cl3(THF)] (11) and [Ti2{{N=PPh2CH2}2C5H3N-2,6}{{471}-Cl)2Cl4(THF)2}]n (12)" --- p.36 / Chapter 2.2.3 --- "Synthesis and Characterization of Iron(II) Complexes [Fe{(2-CH2Py)PR2=NSiMe3}C12] (R = Ph, 13a; Pri, 13b)" --- p.42 / Chapter 2.2.4 --- "Molecular Structures of [Fe{(2-CH2Py)PR2=NSiMe3}Cl2] (R = Ph, 13a; Pri, 13b)" --- p.43 / Chapter 2.2.5 --- "Synthesis and Characterization of Cobalt(II) Complexes [Co{(2-CH2Py)PR2=NSiMe3}Cl2] (R = Ph, 14a; Pri，14b)" --- p.46 / Chapter 2.2.6 --- "Molecular Structures of [Co{(2-CH2Py)PR2=NSiMe3}Cl2] (R = Ph, 14a; Pri, 14b)" --- p.47 / Chapter 2.2.7 --- "Synthesis and Characterization of Copper(I) Complexes [Cu{(2-CH2Py)PPh2=NSiMe3 }I]2 (15a), [Cu{ (2-CH2Py)PPri2=NSiMe3 }I] (15b) and [Cu{2,6-(Me3SiN=PPri2CH2)2C5H3N}]+ [Cul2]-(16)" --- p.50 / Chapter 2.2.8 --- "Molecular Structures of [Cu{(2-CH2Py)PPh2=NSiMe3}I]2 (15a), [Cu{(2-CH2Py)PPri2=NSiMe3} I] (15b) and [Cu{2,6-(Me3SiN=PPri2CH2)2C5H3N}]+ [Cul2]- (16)" --- p.53 / Chapter 2.2.9 --- Spectroscopic properties of compounds 11-16 --- p.58 / Chapter 2.3 --- Experimental Section --- p.60 / Chapter 2.4 --- References --- p.64 / Chapter CHAPTER 3 --- Synthesis and Characterization of Group 8 Transition Metal Complexes Containing Phosphoranoimine Ligands / Chapter 3.1 --- Introduction --- p.65 / Chapter 3.2 --- Results and Discussion / Chapter 3.2.1 --- "Synthesis and Characterization of Nickel(II) Complexes [Ni{(2-CH2Py)PR2=NSiMe3 }Br2] (R = Ph, 17a; Pri, 17b)" --- p.68 / Chapter 3.2.2 --- "Molecular Structures of [Ni{(2-CH2Py)PR2=NSiMe3}Br2] (R = Ph, 17a; Pri, 17b)" --- p.69 / Chapter 3.2.3 --- "Synthesis and Characterization of hydrolyzed Nickel(II) and Palladium(II) Complexes [Ni{2,6-(HN=PPh2CH2)(Me3SiN=PPh2CH2) C5H3N}Br]+[Br]- (18), [(EtOH)Ni{2，6-(HN=PPh2CH2)2- C5H3N}C1]+[C1]- (19) and [Pd{(2-CH2Py)PPh2=NH}Cl2] (20)" --- p.72 / Chapter 3.2.4 --- "Molecular Structures of [Ni{2,6-(HN=PPh2CH2)(Me3SiN=PPh2CH2) C5H3N }Br]+[Br]- (18) and [(EtOH)Ni{2,6-(HN=PPh2CH2)2- C5H3N}C1]+[C1]- (19)，and [Pd{ (2-CH2Py)PPh2=NH}Cl2] (20 )" --- p.75 / Chapter 3.2.5 --- "Synthesis and Characterization of Ionic Palladium(II) Complex [Pd{2,6-(Me3SiN = PPh2CH2)2C5H3N}Cl]+[Cl]- (21)" --- p.80 / Chapter 3.2.6 --- "Molecular Structure of[Pd{2,6-(Me3SiN=PPh2CH2)2C5H3N}Cir[Cir]- (21)" --- p.81 / Chapter 3.2.7 --- Spectroscopic properties of compounds 17-21 --- p.83 / Chapter 3.3 --- Experimental Section --- p.84 / Chapter 3.4 --- References --- p.87 / Chapter CHAPTER 4 --- Reactivity of Phosphoranoimine Complexes on Ethylene Polymerization / Chapter 4.1 --- Introduction / Chapter 4.1.1 --- A Brief Review on Olefin Polymerization --- p.89 / Chapter 4.2 --- Results and Discussion --- p.92 / Chapter 4.3 --- Experimental Section --- p.94 / Chapter 4.4 --- References --- p.95 / APPENDIX I / Crystallographic Data and Refinement Parameters --- p.96 / APPENDIX II / Chapter A. --- General Experimental Procedures and Physical Measurement --- p.105 / Chapter B. --- X-ray Crystallography --- p.105

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

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

[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.

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