Thesis (Ph.D.)--University of Hong Kong, 1997. / Includes bibliographical references (leaf 389-411). Also available in print.

Thesis (Ph. D.)--University of Hong Kong, 1999. / Includes bibliographical references (leaves 291-311).

Thesis (Ph. D.)--University of Hong Kong, 2000. / Includes bibliographical references (leaves 250-279).

Thesis (Ph. D.)--University of Hong Kong, 1997. / Includes bibliographical references (leaf 389-411).

Thesis (Ph. D.)--University of Hong Kong, 1995. / Includes bibliographical references (leaf 230-247).

Thesis (M. Phil.)--University of Hong Kong, 2010. / Includes bibliographical references (leaves 173-174). Also available in print.

No description available.

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

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