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

[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.

Errata inserted in preliminary pages. / Bibliography: leaves 171-184. / 184 leaves : ill. ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / This thesis details the synthesis, characterization and reactions of some transition metal complexes containing ligands derivived from the diacetylenes 1,4-bis (trimethylsilyl)buta-1,3-diyne and buta-1,3-diyne. Some related chemistry of the unsaturated carbone complexes are also explored. / Thesis (Ph.D.)--University of Adelaide, Dept. of Chemistry, 1997

Lai, Yin Man. / Thesis submitted in: November 2008. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2009. / Includes bibliographical references. / Abstracts in English and Chinese. / ACKNOWLEDGEMENT --- p.I / ABSTRACT --- p.II / 摘要 --- p.IV / ABBREVIATIONS --- p.V / LIST OF COMPOUNDS --- p.VI / TABLE OF CONTENTS --- p.IX / Chapter CHAPTER 1 --- A 2-PYRIDYL AMIDO LIGAND CONTAINING A PENTAFLUOROPHENYL SUBSTITUENT --- p.1 / Chapter 1. l --- General Background --- p.1 / Chapter 1.2 --- Examples of Amido Ligands --- p.3 / Chapter 1.3 --- An overview on Amido Ligands Containing Electron-withdrawing Substituents --- p.5 / Chapter 1.4 --- Objectives of This Work --- p.7 / Chapter 1.5 --- Results and Discussion --- p.8 / Chapter 1.5.1 --- Preparation of HLC6F5 (1) and its Potassium Derivatives --- p.8 / Chapter 1.5.2 --- Physical Characterization of Compounds 1-3 --- p.10 / Chapter 1.5.3 --- Molecular Structures of Compounds 2 and 3 --- p.13 / Chapter 1.6 --- Experimentals for Chapter 1 --- p.19 / Chapter 1.7 --- References for Chapter 1 --- p.22 / Chapter CHAPTER 2 --- "ZIRCONIUM(IV), VANADIUM(III) AND CHROMIUM(III) COMPLEXES DERIVED FROM THE [N(C6F5)(2-CsH3N-6-ME)] LIGAND" --- p.27 / Chapter 2.1 --- "An Overview on Zr(IV), V(III) and Cr(III) Complexes Supported by 2-Pyridyl Amido Ligands" --- p.27 / Chapter 2.2 --- Recent Results from our Group --- p.32 / Chapter 2.3 --- Objectives of this work --- p.33 / Chapter 2.4 --- "Synthesis and Structures of Tris(amido) Complexes of Zr(IV), V(III) and CR(III)" --- p.34 / Chapter 2.4.1 --- "Synthesis of [Zr(LC6F5)3(Cl) ´Ø C7H8] (4), V(LC6F5)3 (5) and [Cr(LC6F5)3] (6)" --- p.34 / Chapter 2.4.2 --- Molecular Structures of [Zr(LC6F5)3(Cl)´ØC7H8] (4)f and [Cr(LC6F5)3] (6) --- p.37 / Chapter 2.5 --- Experimentals for Chapter 2 --- p.43 / Chapter 2.6 --- References for Chapter 2 --- p.45 / Chapter CHAPTER 3 --- "MANGANESE(II), IRON(II), COBALT(II) AND NICKEL(II) COMPLEXES OF THE [N(C6F5)(2-C5H3N-6-ME)] LIGAND" --- p.49 / Chapter 3.1 --- A Brief Review on Amides of the Late Transition Metals --- p.49 / Chapter 3.2 --- Examples of Late Transition Metal Complexes Supported by 2-Pyridyl Amido Ligands --- p.51 / Chapter 3.3 --- Objectives of our studies --- p.53 / Chapter 3.4 --- "Synthesis and Structures of Bis(amido) Complexes of Mn(II), Fe(II), Co(II) and NI(II)" --- p.54 / Chapter 3.4.1 --- "Synthesis of [M(LC6F5)2(tmeda)] (M = Mn (7), Fe (8), Co (9), Ni (10)]" --- p.54 / Chapter 3.4.2 --- Molecular Structures of Complexes 7-10 --- p.57 / Chapter 3.5 --- "Synthesis, Structure and Reactivity of a Mono(amido) Fe(II) Complex" --- p.61 / Chapter 3.5.1 --- Synthesis of [Fe(LC6F5)(CI)(tmeda)](11) --- p.61 / Chapter 3.5.2 --- Physical Characterization of Compound 11 --- p.62 / Chapter 3.5.3 --- Molecular Structures of Compound 11 --- p.62 / Chapter 3.5.4 --- Reactivity Studies of [Fe(LC6F5)(Cl)(tmeda)] (11) --- p.66 / Chapter 3.6 --- Synthesis of Fe(III) Tri(amido) Complex --- p.69 / Chapter 3.7 --- Experimentals for Chapter 3 --- p.70 / Chapter 3.8 --- References for Chapter 3 --- p.73 / Chapter CHAPTER 4 --- SUMMARY OF THE PRESENT RESEARCH WORK --- p.75 / TABLE OF APPENDIX --- p.79 / "General Procedures, Physical Measurements and X-Ray Structural Analysis" --- p.80 / 1HNMR of HCC6F5(1) --- p.82 / 13CNMR of HLC6F5(1) --- p.83 / 19FNMR of HLC6F5(1) --- p.84 / 1HNMR of [K(LC6F5)(tmeda)]2 (2) --- p.85 / 13CNMR OF [K(LC6F5)(tmeda)]2 (2)) --- p.86 / 19FNMR of [K(LC6F5)(TMEDA)]2 (2)) --- p.87 / 1HNMR of [K(LC6F5)(thf)2]2 (3) --- p.88 / 13CNMR of [K(LC6F5)(thf)2]2 (3) --- p.89 / 19FNMR OF [K(LC6F5)(THF)2]2 (3) --- p.90 / 1HNMR of Zr(LC6F5)3(Cl).(C7H8)] (4) --- p.91 / Selected crystallographic data of complexes 2 and 3 --- p.94 / Selected crystallographic data of complexes 4 and 6 --- p.95 / Selected crystallographic data of complexes 7 and 8 --- p.96 / Selected crystallographic data of complexes 9 and 10 --- p.97 / Selected crystallographic data of complex 11 --- p.98

New classes of luminescent transition metal complexes, including the systems of rhenium(I) tricarbonyl diimine, cyclometalated iridium(III) diimine, cyclometalated rhodium(III) diimine, ruthenium(II) diimine and ruthenium(II) terpyridine complexes tethered with rhodamine moieties, have been synthesized. The X-ray crystal structure of one of the cyclometalated rhodium(III) diimine complexes with rhodamine pendants, [Rh(SPLC2N2)(ppy)2](PF6) has been determined. The molecular structure of [Rh(SPLC2N2)(ppy)2](PF6) showed a distorted octahedral geometry and the rhodamine moiety was found in a spirolactam closed-ring form. All of them were found to exhibit emission in fluid solution. The emissions of rhenium(I) tricarbonyl diimine and ruthenium(II) polypyridyl complexes are derived from the triplet metal-to-ligand charge transfer (3MLCT) excited state, i.e. from dπ orbital of the rhenium(I) or ruthenium(II) metal center to the π* orbital of the diimine ligand; while that of cyclometalated iridium(III) diimine complexes is (3MLCT) [dπ(Ir) → π*(N^N)] and that of cyclometalated rhodium(III) diimine complexes involves the (3IL) [π → π*(N^C)] excited state, probably mixed with (3MLCT) [dπ(Rh) → π*(N^C)] character. The cation-binding properties of these complexes toward alkali, alkaline-earth and transition-metal cations were investigated by electronic absorption and emission spectrophotometries. Some of them were found to exhibit new low-energy absorption and emission bands, characteristic of the rhodamine absorption and emission, with high selectivity and sensitivity for certain transition metal cations. A series of rhodamine-appended Schiff base organic compounds has also been synthesized in order to explore their capability as luminescent lanthanide ion sensors. The lanthanide ion binding properties of one of the compounds in acetonitrile were examined. Upon addition of lanthanide ions, new intense low-energy electronic absorption and emission bands were also observed, characteristic of the rhodamine absorption and emission, demonstrating its lanthanide ion sensing behaviour. / published_or_final_version / Chemistry / Master / Master of Philosophy

published_or_final_version / abstract / Chemistry / Doctoral / Doctor of Philosophy

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

by Shan-Ming Kuang. / Thesis (Ph.D.)--Chinese University of Hong Kong, 1998. / Includes bibliographical references (p. 135-152). / 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.