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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by Lam Fung. / Thesis (M.Phil.)--Chinese University of Hong Kong, 1994. / Includes bibliographical references (leaves 70-75). / Acknowledgements --- p.i / Abbreviations --- p.ii / Abstract --- p.iii / Introduction --- p.1 / Results and Discussion --- p.16 / Conclusion --- p.55 / Experimental --- p.56 / References --- p.70 / Appendix --- p.76 / List of Spectra --- p.80

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

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