本研究主要集中在苯胺基配體及全氟苯胺基配體　[N(R')(2,6-R₂C₆H₃)]⁻ [R = Me, Pr{U+2071} ; R' = SiMe₃, SiBu{U+1D57}Me₂, C₆F₅]　衍生出來的一價銅的配位化學，包括其絡合物的合成、結構及氧化反應的研究。 / 第一章概括地介紹了金屬胺他物及銅配合物氧化反應的研究背景。 / 第二章敘述了由苯胺基配體所衍生的一價銅絡合物的裝備及結構。透過苯胺基鹼金屬絡合物 [(M)N(R')(2,6-R₂C₆H₃)] (M = Li, K) 與銅鹵化物CuX (X = Cl, I) 反應，成功合成一系列一價銅絡合物 [Cu₂(L¹)₂(tmeda)] (L¹= [N(SiMe₃)(2,6-Me₂C₆H₃)]⁻)⁻ 及[{Cu(tmeda)₂}{Cu(L{U+207F})₂}] (L{U+207F} = [N(R')(2,6-R₂C₆H₃)]⁻: n = 2, R = Pr{U+2071}, R' = SiMe₃; n = 3, R = Me, R' = SiBu{U+1D57}Me₂; n = 4, R = Pr{U+2071}, R' = SiBu{U+1D57}Me₂; n = 5, R = Me, R' = C₆F₅; n = 6, R = Pri, R' = C₆F₅)。另外，銅碘化物與兩倍的苯胺基鉀絡合物反應[KN(R')(2,6-R₂C₆H₃)] 生成一價銅絡合物 [(tmeda)KCu(L²)₂] (L² = [N(SiMe₃)(2,6-Pr{U+2071} ₂C₆H₃)]) 及 [(tmeda)₂KCu(L⁶)₂] (L⁶ = [N(C₆F₅)(2,6-Pr{U+2071} ₂C₆H₃)]。 / 第三章描述了苯胺基一價銅絡合物跟三苯基膦的氧化反應研究，其中研究不同反應條件，包括反應溫度、氧含量及催化物比例對氧化反應的影響。 / 第四章總結了本研究的成果，同時簡單討論了本課題未來的研究方向。 / The present research work focuses on the synthesis, structure and oxygenation reactivity of a series of copper(I) complexes supported by [N(R')(2,6-R₂C₆H₃)]⁻ (R = Me, Pri ; R' = SiMe₃, SiBu{U+1D57}Me₂, C₆F₅) ligands. / Chapter one gives an overview on the chemistry of metal amides. A brief introduction to copper-dioxygen chemistry is also presented. / Chapter two describes the synthesis and structural characterisation of copper(I) anilides. A series of anilido ligands of the type [N(R')(2,6-R₂C₆H₃)]⁻ (R = Me, Pr{U+2071} ; R' = SiMe₃, SiBu{U+1D57}Me₂, C₆F₅) and tmeda (N,N,N',N'-tetramethylethylenediamine) were employed in our studies. Reactions of CuX (X = Cl, I) with alkali-metal salts of the [N(R')(2,6-R₂C₆H₃)]⁻ ligands yielded the corresponding copper(I) complexes of the type [Cu₂(L¹)₂(tmeda)] (L¹= [N(SiMe₃)(2,6-Me₂C₆H₃)]⁻) or [{Cu(tmeda)₂}{Cu({U+207F})₂}] (L{U+207F} = [N(R')(2,6-R₂C₆H₃)]⁻: n = 2, R = Pr{U+2071}, R' = SiMe₃; n = 3, R = Me, R' = SiBu^(t)Me₂; n = 4, R = Pri, R' = SiBu{U+1D57}Me₂; n = 5, R = Me, R' = C₆F₅; n = 6, R = Pri, R' = C₆F₅). Moreover, reactions of CuI with two equivalents of potassium salts of the [N(R')(2,6-R₂C₆H₃)]⁻ ligands gave copper(I) complexes of the type [(tmeda)KCu(L²)₂] (L₂ = [N(SiMe₃)(2,6-Pr{U+2071} ₂C₆H₃)]) and [(tmeda)₂KCu(L⁶)₂] (L⁶ = [N(C₆F₅)(2,6-Pr{U+2071} ₂C₆H₃)]. / Chapter three deals with the oxygenation reactivity of the copper(I) anilido complexes prepared in this work. The reactions of copper(I) complexes 17-24 with dioxygen led to the conversion of triphenylphosphine to triphenylphosphine oxide. The oxo-transfer reaction was studied under different reaction conditions, such as reaction temperature, oxygen content, and [PPh₃]:[complex] ratio. / Chapter four summarises the results of this research work. An outlook on future directions of this research project is also described in this chapter. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Chen, Yat Kit. / "November 2012." / Thesis (M.Phil.)--Chinese University of Hong Kong, 2013. / Includes bibliographical references. / Abstracts also in Chinese. / Abstract --- p.i / 摘要 --- p.iii / Acknowledgement --- p.iv / Abbreviations --- p.vii / List of Compounds --- p.x / Chapter Chapter 1 - --- An Overview on Late Transition Metal Amides and Copper-Dioxygen Chemistry / Chapter 1.1 --- General Background --- p.1 / Chapter 1.2 --- An Introduction to Late Transition Metal Amides --- p.1 / Chapter 1.3 --- An Introduction to Copper-Dioxygen Chemistry --- p.4 / Chapter 1.4 --- Objectives of This Work --- p.6 / Chapter 1.5 --- References for Chapter 1 --- p.7 / Chapter Chapter 2 - --- Synthetic and Structural Studies of Copper Anilides / Chapter 2.1 --- A General Overview on Anilido Complexes --- p.11 / Chapter 2.2 --- Aims of Our Study --- p.22 / Chapter 2.3 --- Results and Discussion / Chapter 2.3.1 --- Aniline Precursors and Their Alkali Metal Derivatives / Chapter 2.3.1.1 --- Synthesis of Aniline Precursors HL{U+207F} (n = 1-6) --- p.23 / Chapter 2.3.1.2 --- Synthesis of Alkali Metal Derivatives of L{U+207F} (n = 1-6) --- p.25 / Chapter 2.3.1.3 --- Physical Properties of Compounds 7-16 --- p.26 / Chapter 2.3.1.4 --- Molecular Structures of Compounds 7-16 --- p.33 / Chapter 2.3.2 --- Synthesis and Structures of Copper Anilides / Chapter 2.3.2.1 --- Synthesis of Copper(I) Complexes of L{U+207F}(n = 1-6) --- p.62 / Chapter 2.3.2.2 --- Physical Properties of Compounds 17-24 --- p.65 / Chapter 2.3.2.3 --- Molecular Structures of Compounds 17-24 --- p.70 / Chapter 2.3.3 --- Electrochemical Studies --- p.100 / Chapter 2.4 --- Experimentals for Chapter 2 --- p.109 / Chapter 2.5 --- References for Chapter 2 --- p.120 / Chapter Chapter 3 - --- Oxygenation Reactivity Studies / Chapter 3.1 --- A General Review on Oxygenation Copper-Dioxygen Chemistry --- p.128 / Chapter 3.2 --- Aims of Our Study --- p.148 / Chapter 3.3 --- Results and Discussion --- p.149 / Chapter 3.4 --- Experimentals for Chapter 3 --- p.153 / Chapter 3.5 --- References for Chapter 3 --- p.155 / Chapter Chapter 4 - --- Summary and Future Directions --- p.161 / Chapter Appendix A --- General Procedure, Physical Measurements and X-ray Diffraction Analysis --- p.164 / Chapter Appendix B --- NMR Spectra of Compounds --- p.166 / Chapter Appendix C --- Selected Crystallographic Data --- p.191

a series of complexes of the type MLnX where M=Cu(II), Ni(II), and Cr(III), L=β-diketonate (n=1 for Cu (II) and Ni(II), n=2 for Cr(III)) and X=bridging anion was synthesized in order to study the effect of the bridging group on the magnetic exchange interaction parameter, J.

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

This thesis continues the study into the synthesis and analysis of metal poly - yndiyl complexes. These molecules have shown promise as model molecular wires. The study provides a general overview of the interest in carbon based molecules and introduces the need for molecular electronics. Some of the most promising classes of molecular wires are described before outlining the methods of evaluation. / Thesis (Ph.D.)--School of Chemistry and Physics, 2006.

Thesis (Ph. D.)--University of Wyoming, 2006. / Title from PDF title page (viewed on Dec. 20, 2007). Includes bibliographical references.

Graduation date: 2003

Free radical cyclization methodology has been used extensively in synthesis for manipulation of complex molecules such as alkaloids, terpenes, carbohydrates, peptides and nucleic acids. The methodology has emerged as a result of work by physical organic chemists who determined rate constants for the most common radical reactions used in organic synthesis. A novel route to cyclic imines based on 5-exo radical cyclization was explored. The radical precursors were imines prepared from allylamine and readily available a-phenylselenenyl ketones. The synthesis of conformationally constrained bicyclic nucleosides is also reported using 5-exo and 6-exo cyclizations of hexenyl and heptenyl radicals in thymidine nucleosides. The nucleosides were incorporated in a 15mer antisense oligonucleotide via solid-phase oligonucleotide synthesis. The AONs with the modifications were tested for target affinity and stability and compared with the well known LNA modified AONs. The thesis discusses the unique qualities of these novel molecules and presents them as potential candidates for antisense therapeutic agents. Keeping up with the theme of intramolecular carbon-carbon bond formation, microwave induced carbodechalcogenation of chalcogenoanhydrides was explored. Poor generality in these reactions made us turn to transition metal catalysis for Sonogashira cross-coupling reactions using alkyl aryl and diaryl tellurides as coupling partners.

The development of a palladium-catalyzed intramolecular carboesterification of unactivated olefins is described. Olefin difunctionalization is a powerful tool for adding complexity to a molecule, and this formal [3+2] cycloaddition generates highly functionalized fused ring systems. Initially discovered by Dr. Yang Li in our group, it was found that when propiolic acids with a pendant terminal olefin were treated with 1 mol % Pd(MeCN)2Cl2, 3 equivalents of copper (II) chloride, and 3 equivalents of lithium chloride in acetonitrile at 50 °C, cyclization occurred in up to 90% yield. The optimization of this reaction and the extension to propiolamides and propargyl alcohols is described in this thesis. A mechanism involving a novel palladium-carboxylate species is proposed. Preliminary investigations into the synthesis of chiral sulfoxide pincer ligands are also described. The nucleophilic aromatic substitution of 1,3-dibromobenzene and 2,6-dichloropyridine with various thiols, followed by oxidation of the sulfides to sulfoxides is investigated as a route to the desired proligands.

The development of a palladium-catalyzed intramolecular carboesterification of unactivated olefins is described. Olefin difunctionalization is a powerful tool for adding complexity to a molecule, and this formal [3+2] cycloaddition generates highly functionalized fused ring systems. Initially discovered by Dr. Yang Li in our group, it was found that when propiolic acids with a pendant terminal olefin were treated with 1 mol % Pd(MeCN)2Cl2, 3 equivalents of copper (II) chloride, and 3 equivalents of lithium chloride in acetonitrile at 50 °C, cyclization occurred in up to 90% yield. The optimization of this reaction and the extension to propiolamides and propargyl alcohols is described in this thesis. A mechanism involving a novel palladium-carboxylate species is proposed. Preliminary investigations into the synthesis of chiral sulfoxide pincer ligands are also described. The nucleophilic aromatic substitution of 1,3-dibromobenzene and 2,6-dichloropyridine with various thiols, followed by oxidation of the sulfides to sulfoxides is investigated as a route to the desired proligands.

The reactions and photochemistry of atomic and diatomic transition metals with methanol, water, hydrogen, and carbon monoxide in noble gas matrices at cryogenic temperatures have been studied with the use of Fourier Transform infrared inert matrix spectroscopy. Atoms and dimers of iron and cobalt reacted with methanol to form the adducts, M(CH30H) and M2(CH30H), respectively. M(CH30H) underwent metal insertion into the 0-H bond of methanol to yield methoxymetal hydride, CH3OMH, with irradiation of the matrix in the violet (400 nm < λ < 500 nm) region. Ultraviolet (280 nm < λ < 360 nm) photolysis of the matrix rearranged CH30MH to yield the methylmetal hydroxide species, CH3MOH. CH30MH dissociated into carbon monoxide and hydrogen after prolonged irradiation in the ultraviolet region. Surprisingly, nickel atoms reacted spontaneously to insert into the 0-H bonds of methanol and water to form CH30NiH and HONiH, respectively. Violet photolysis caused CH30NiH to rearrange to form methylnickel hydroxide, CH3NiOH. This is effectively a two step process of the C-0 activation of methanol by a nickel atom. In addition to rearrangement, CH30NiH dissociates into carbon monoxide and hydrogen with violet photolysis. Nickel dimers also reacted spontaneously with water to form both an adduct and insertion products. Atomic nickel spontaneously inserts into the H-H bond of molecular hydrogen to yield a bent nickel dihydride, NiH2, in krypton and xenon matrices. Nickel dimers and trimers insert into the H-H bond of hydrogen to form Nix(H)2. In addition to the insertion products, nickel atoms, dimers, and trimers form adducts molecularly with hydrogen to yield complexes of the form Nix(H2)y, where x or y = 1-3. Reactions of iron with carbon monoxide in an argon matrix yielded the iron-carbonyl complexes, Fex(CO)y, where x = 1-3 and y = 1-2.