Thesis (Ph.D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 1980. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND SCIENCE. / Includes bibliographical references. / by Jere Douglas Fellmann. / Ph.D.

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Thesis. 1975. Ph.D.--Massachusetts Institute of Technology. Dept. of Chemistry. / Vita. / Includes bibliographical references. / Ph.D.

Chong Kim Hung. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2005. / 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 --- p.ix / Synthesized / Abbreviations --- p.x / Chapter Chapter 1 --- Reactivity of Pyridyl-1-azaallyl Enamido Germanium(II) Chloride / Chapter 1.1 --- Introduction --- p.1 / Chapter 1.1.1 --- General Aspects of Reactivity of Heteroleptic Germylenes --- p.1 / Chapter 1.1.2 --- Synthesis of Pyridyl-1 -azaallyl Germanium(II) Chloride Complex --- p.10 / Chapter 1.1.3 --- Objectives of This Work --- p.12 / Chapter 1.2 --- Results and Discussion --- p.14 / Chapter 1.2.1.1 --- Synthesis of Chalcogenonyl Halide Complexes --- p.15 / Chapter 1.2.1.2 --- Spectroscopic Properties of 33 and 34 --- p.15 / Chapter 1.2.1.3 --- "Molecular Structures of [Ge(E){N(SiMe3)C(Ph)- C(SiMe3)(C5H4N-2)}Cl] (E = S (33), Se (34))" --- p.16 / Chapter 1.2.2.1 --- Synthesis of Group 11 Transition Metal-Pyridyl-1- Enamido Germanium(II) Chloride Complexes --- p.20 / Chapter 1.2.2.2 --- Spectroscopic Properties of 35 and 36 --- p.21 / Chapter 1.2.2.3 --- Molecular Structures of [Ge(CuI){N(SiMe3)- C(Ph)C(SiMe3)(C5H4N-2)}Cl(THF)2]4 (35) and [Ge(AuI){N(SiMe3)C(Ph)C(SiMe3)(C5H4N-2)}Cl] (36) --- p.22 / Chapter 1.2.3.1 --- "Reaction of Pyridyl-l-azaallyl Germanium(II) Chloride with 3,5-di-tert butyl-o-benzoqumone: Synthesis of [Ge{O(2,4-di-Bu'-C6H2)O}{N(SiMe3)C(Ph)C(SiMe3)- (C5H4N-2)}C1] (37)" --- p.27 / Chapter 1.2.3.2 --- Spectroscopic Properties of 37 --- p.27 / Chapter 1.2.3.3 --- "Molecular Structure of [Ge{0(2,4-di-Bu'- C6H2)O} {N(SiMe3)C(Ph)C(SiMe3)(C5H4N-2)}Cl] (37)" --- p.28 / Chapter 1.2.4.1 --- Synthesis of Boron-Germanium(II) Hydride Adduct --- p.31 / Chapter 1.2.4.2 --- Spectroscopic Properties of 38 --- p.31 / Chapter 1.2.4.3 --- Molecular Structure of [Ge(BH3){N(SiMe3)C(Ph)- C(SiMe3)(C5H4N-2)}H] (38) --- p.32 / Chapter 1.2.5.1 --- Substitution Reaction of Pyridyl-l-azaallyl Germanium(II) Chloride with Lithium Phenylacetylide --- p.34 / Chapter 1.2.5.2 --- Spectroscopic Properties of 39 --- p.34 / Chapter 1.2.5.3 --- Molecular Structure of [Ge{N(SiMe3)C(Ph)C(SiMe3)- (C5H4N-2)}(CCPh)] (39) --- p.35 / Chapter 1.2.6.1 --- Reaction of Pyridyl-l-azaallyl Germanium(II) Chloride with excess lithium; the formation of [GeC(Ph)C(SiMe3)(C5H4N-2)]2 (40) --- p.38 / Chapter 1.2.6.2 --- Spectroscopic Properties of 40 --- p.38 / Chapter 1.2.6.3 --- Molecular Structure of [GeC(Ph)C(SiMe3)(C5H4N-2)]2 (40) --- p.39 / Chapter 1.3 --- Experimental for Chapter 1 --- p.43 / Chapter 1.4 --- References for Chapter 1 --- p.50 / Chapter Chapter 2 --- Synthesis of Late Transition Metal Pyridyl-l-azaallyl Complexes / Chapter 2.1 --- Introduction --- p.55 / Chapter 2.1.1 --- General Aspects of 1 -azaallyl Metal Complexes --- p.55 / Chapter 2.1.2 --- Synthesis of Pyridyl-l-azaallyl Metal Complexes --- p.61 / Chapter 2.2 --- Results and Discussion --- p.68 / Chapter 2.2.1 --- Synthesis of Late Transition Metal Pyridyl-l-azaallyl Complexes --- p.68 / Chapter 2.2.2 --- Spectroscopic Properties of 55-59 --- p.70 / Chapter 2.2.3 --- Molecular Structures of Compounds 55-59 --- p.71 / Chapter 2.3 --- Experimental for Chapter 2 --- p.80 / Chapter 2.4 --- References for Chapter 2 --- p.83 / Appendix I / Chapter A. --- General Procedures --- p.86 / Chapter B. --- Physical and Analytical Measurements --- p.86 / Appendix II / Table A.1. Selected Crystallographic Data for Compounds 33-36 --- p.89 / Table A.2. Selected Crystallographic Data for Compounds 37-40 --- p.90 / Table A.3. Selected Crystallographic Data for Compounds 56-58 --- p.91 / Table A.4. Selected Crystallographic Data for Compound 59 --- p.92

Chapter 1 gives a brief introduction to metal complexes supported by anionic nitrogen-based ligands. / Chapter 2 describes the synthesis, structural characterization and reactivity of Mn(II), Fe(II) and Co(II) amides derived from the strongly electron-withdrawing [N(C6F5)(C6H3Pr i2-2,6)]- ligand (L 1). Twelve new compounds, including the ligand precursor HL 1, and three alkali-metal and eight late transition metal derivatives of L1, were prepared. Reactions of MCl2 (M = Mn, Fe, Co) with [Li(L1)(TMEDA)] (2) yielded the monoamido complexes [M(L1)Cl(TMEDA)] [M = Mn (5), Fe ( 6), Co (7)]. Treatment of [Li(L1)(THF) 3] with MCl2 (M = Fe, Co) afforded the diamido complexes [M(L1)2(mu-Cl)Li(THF)3] [M = Fe ( 8), Co(9)]. The reaction chemistry of the Co(II) complex 7 was investigated. Treatment of the Co(II) derivative 7 with LiMe, NaN3 and NaOMe gave the corresponding methyl-, azido- and methoxide-amide complexes, namely [Co(L1)(Me)(TMEDA)] ( 10), [Co(L1)(N3)(TMEDA)] (11) and [Co(L1)2(mu-OMe)Na(TMEDA)] (12), respectively. The solid-state structures of complexes 5--12 were determined by X-ray crystallography. / Chapter 3 reports on the synthesis and catalytic properties of lanthanide(III) complexes derived from the unsymmetrical [PhC(NSiMe3)(NC6 H3Pri2-2,6)] - ligand (L2). The lithium and potassium salts of L2, and eight lanthanide(III) derivatives of L2 were synthesized. A series of Ln(III) complexes of the general formula [Ln(L 2)2(mu-Cl)2Li(TMEDA)] [Ln = Y (17), Eu (18), Er (19), Lu (20)] and [Li(THF) 4][Ln(L2)2Cl2] [Ln = Ce ( 21), Nd (22), Sm (23)] were synthesized by the reactions of anhydrous LnCl3 with two molar equivalents of [Li(L2)(TMEDA)] (15). In addition, the neutral dimeric yttrium(III) complex [Y(L2)2(mu-Cl)] 2 (24) was also prepared by the reaction of anhydrous YCl 3 with the potassium amidinate [K(L2)]n (16). The catalytic properties of complexes 20--22 towards the ring-opening polymerization of epsilon-caprolactone were also studied in this work. / Chapter 4 reports on the coordination chemistry of L2 towards divalent lanthanide metal ions. Three neutral divalent lanthanide complexes, [Ln(L2)2(THF)n] [Ln = Sm, n = 2 (25); Ln = Eu, n = 2, (26); Ln = Yb, n = 1 (27)], were prepared by treatment of LnI2(THF) 2 with the potassium amidinate [K(L2)]n . The reaction chemistry of 25--27 as one-electron transfer reagents has been examined. This led to the isolation of six lanthanide(III) complexes (28--33). Treatment of 25--27 with PhEEPh (E = Se, Te) gave the corresponding Ln(III) chalcogenolate complexes [Ln(L2)2(mu-EPh)]2 [Ln = Sm, E = Se (28); Ln = Eu, E = Se (29); Ln = Sm, E = Te ( 31)] and [Yb(L2)2(SePh)(THF)] (30). Besides, the reaction of 27 with iodine resulted in the isolation of the iodide complex [Yb(L2)2(I)(THF)] ( 32), whilst treatment of 25 with dicyclohexylcarbodiimide led to [Sm(L2)2{CyNC(H)NCy}] (33). / Chapter 5 summarizes the results of this research work. A brief suggestion on future directions of this research project is also discussed. / The present research work was focused on the coordination chemistry of the highly electron-withdrawing [N(C6F5)(C6H 3Pri2-2,6)]- ligand and the unsymmetrical [PhC(NSiMe3)(NC6H 3Pri2-2,6)- ligand. The first part of this work was centered on the synthesis, structure and reactivity of late transition metal complexes supported by the [N(C6F5)(C6H3Pr i2-2,6)]- ligand (L 1). The second part of this work dealed with the chemistry of trivalent and divalent lanthanide complexes derived from the bulky [PhC(NSiMe3 )(NC6H3Pri 2-2,6)]- ligand (L2). / Yao, Shuang. / Adviser: Hung Kay Lee. / Source: Dissertation Abstracts International, Volume: 71-01, Section: B, page: 0317. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2009. / Includes bibliographical references. / 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 Company, [200-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstracts in English and Chinese.

Abstract not available. / Qiu, Zaozao. / Adviser: Zuowes Xie. / Source: Dissertation Abstracts International, Volume: 73-02, Section: B, page: . / Thesis (Ph.D.)--Chinese University of Hong Kong, 2010. / Includes bibliographical references (leaves 150-161). / 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.

Alkylation of [eta5:sigma-Me2C(C5 H4)(C2B10H10)]TiCl(NMe 2) generates [eta5:sigma-Me2C(C5 H4)(C2B10H10)]Ti(R)(NMe 2) (R = Me, CH2TMS), which offers a unique opportunity to observe the direct competition among Ti-C(alkyl), Ti-N and Ti-C(cage) bonds in the insertion reactions with unsaturated molecules. The results indicate that unsaturated molecules insert preferably into the Ti-C (alkyl) bond over the Ti-N bond, while the Ti-C (cage) bond remains intact in all reactions. Several imido-titanium complexes [eta5:sigma-Me2C(C 5H4)(C2B10H10)]Ti(=NR)(Py) and [eta5:sigma-Me2C(C9H6)(C 2B10H10)]Ti(=NtBu)(Py) have been prepared by salt metathesis reactions or imido exchange reactions. These imido complexes can react with a variety of unsaturated molecules to give imido exchange products or [2+2] cycloaddition species. The imido complex [eta5:sigma-Me2C(C5H4)(C 2B10H10)]Ti(=NtBu)(Py) can also catalyze the hydroamination of phenyl acetylene. The key intermediate metallacyclic complex has been isolated and structurally characterized. / By taking the advantage of a cyclic organic group and an icosahedral carborane as well as the bridging ligand, trivalent phosphorus-bridged ligand iPr2NP(C9H7)(C2B 10H11) is designed and successfully synthesized. It is readily converted into the corresponding mono- and di-lithium salts, which have found many applications in transition metal chemistry. A series of organolanthanide and group 4 metal complexes derived from this new ligand have been prepared and structurally characterized. It is found that this ligand can effectively prevent lanthanocene chlorides from ligand redistribution reactions. [eta 5:sigma-iPr2NP(C 9H6)(C2B10H10)]Zr(NMe 2)2 can catalyze ethylene polymerization upon activation with MMAO and initiate the polymerization of epsilon-caprolactone. / iPr2NP(C9H 7)(C2B10H11) can be converted into the pentavalent derivative iPr2NP(O)(C9H 7)(C2B10H11) by treatment with H 2O2. Interactions of M(NMe2)4 with iPr2NP(O)(C9H7)(C2 B10H11) give unexpected products [sigma.sigma- iPr2NP(O)(C9H6)(C2 B10H11)]M(NR2)2. To investigate the similarities and differences between iPr2NP(O)(C 9H7)(C2B10H11) and its fluorenyl derivative in chemical properties, iPr 2NP(O)(C13H9)(C2B10H 11) is also prepared in a similar manner. It reacts easily with Zr(NMe 2)4 to give the amine elimination product [sigma.sigma- iPr2NP(O)(C13H8)(C 2B10H10)]Zr(NMe2)2(THF). However, treatment of iPr2NP(O)(C 2B10B11)(C2B10H11) with Ti(NMe2)4 affords amine elimination/deboration complex [sigma:eta5-iPr 2NP(O)(C13H9)(C2B9H 10)]Ti(NMe2)2. / Wang Hong. / "February 2005." / Adviser: Xie Zuomei. / Source: Dissertation Abstracts International, Volume: 67-01, Section: B, page: 0265. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2005. / Includes bibliographical references (p. 168-180). / 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, [200-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstracts in English and Chinese. / School code: 1307.

Lo, Kwok Cheung. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2009. / Includes bibliographical references (leaves 114-118). / Abstracts in English and Chinese. / Thesis / Assessment Committee --- p.ii / ABSTRACT --- p.iii / ACKNOWLEDGEMENTS --- p.v / TABLE OF CONTENT --- p.vi / Chapter Chapter 1 --- Introduction --- p.1 / Chapter Chapter 2 --- Theoretical Background --- p.5 / Chapter Chapter 3 --- Results --- p.38 / Chapter Chapter 4 --- Discussion and Concluding Remarks --- p.85 / LIST OF TABLES / Table / Table la Electronic energies and geometrical parameters of scandium dicarbide by B3LYP/LANL2DZ and B3LYP/LANL2DZ-d --- p.41 / Table lb Comparison of literature results with current computational results of cyclic scandium dicarbide at equilibrium state by B3LYP/LANL2DZ and B3LYP/LANL2DZ-d --- p.42 / Table lc Comparison of literature results with current computational results of linear scandium dicarbide at equilibrium state by B3LYP/LANL2DZ and B3LYP/LANL2DZ-d --- p.43 / Table 2a Electronic energies and geometrical parameters of titanium --- p.46

本項研究工作主要對五個結構類似的胍基配體， 即 [(2,6-Me₂C₆H₃N)C(NHPri)(NPri)]⁻ (L¹)， [(2,6-Me₂C₆H₃N)C(NHCy)(NCy)]⁻ (L²)， [(2,6-Me₂C₆H₃N)C{N(SiMe₃)Cy}(NCy)]⁻ (L³)， [(2,6-Pri₂C₆H₃N)C{N(SiMe₃)₂}(NC₆H₃Pri₂-2,6)]⁻ (L⁴) 和 [(2,6-Pri₂C₆H₃N)C(NEt₂)(NC₆H₃Pri₂-2,6)]⁻ (L⁵) 與二價鉻以及二價鑭系金屬[Sm(II)、Eu(II) 及 Yb(II)] 的配位化學進行研究，同時，一系列由 L¹ 配體所衍生的三價鑭系金屬配合物亦成功被合成。 / 第一章概括介紹了由胍基配體所構築的金屬配合物的研究背景。 / 第二章敍述了含 L¹ 與 L⁴ 的二價鉻配合物的合成、結構及其化學反應。 通過胍基鉀化合物 [KL¹･0.5PhMe] (1) 與二氯化鉻反應可得到單核二價鉻雙胍基配合物 [Cr(L¹)₂] (3)。 通過胍基鋰化合物 [LiL⁴(Et₂O)] (2) 與二氯化鉻反應，成功製備了單胍基二價鉻配合物 [Cr(L⁴)(μ-Cl)₂Li(THF)(Et₂O)] (4)。 而把二價鉻配合物 4於甲苯溶液中重結晶可得到二聚體的二價鉻配合物 [{Cr(L⁴)(μ-Cl)}₂] (5)。 另外，我們對二價鉻配合物 3 及 4 的反應特性也進行了研究。 [Cr(L¹)₂] (3) 與單質碘、二苯基硫族化合物 PhEEPh (E = S, Se, Te) 以及叠氮金剛烷反應可得相對應的三價鉻混合配體化合物，分別爲 [Cr(L¹)₂I] (6)、[Cr(L¹)₂(EPh)] [E = S (7), Se (8), Te (9)]，及四價鉻配合物 [Cr(L¹)₂{N(1-Ad)}] (10)。 透過單胍基二價鉻配合物 [Cr(L⁴)(μ-Cl)₂Li(THF)(Et₂O)] (4) 與 NaOMe反應可得甲氧基-胍基配合物 [{Cr(L⁴)(μ-OMe)}₂] (11)。 / 第三章主要報導含 L¹， L²， L³ 和 L⁵ 配基的二價鑭系配合物的合成、結構和化學反應特性。 透過 [LnI₂(THF)₂] (Ln = Sm, Eu, Yb) 與胍基鉀鹽反應，我們成功合成一系列二價鑭系絡合物，包括 [{Eu(L¹)(μ-L¹)}₂] (15)， [{Ln(L²)(μ-L²)}₂･nC₆H₁₄] [Ln = Eu, n = 2 (16); Ln = Yb, n = 0 (17)，[Yb(L²)₂(THF)₂] (18)， [Ln(L³)₂(THF)₂･0.25C₆H₁₄] [Ln = Eu (19), Yb (20)]， [{Sm(L³)(μ-I)(THF)}₂] (21) 和 [Sm(L⁵)₂] (22)。 本章亦同時探討二價鑭系配合物15， 18， 20 和 22 作爲還原劑的化學反應特性。 配合物 15 與單質碘反應可得三價銪配合物 [{Eu(L¹)₂(μ-I)}₂] (23)。 配合物 18 與二苯基硫族化合物 PhEEPh (E = S, Se) 反應，可得相對應的三價鐿配合物 [{Yb(L²)₂(μ-EPh)}₂] [E = S (24), Se (25)]。 18 與氯化亞銅反應得到三價鐿配合物 [{Yb(L²)₂(μ-Cl)}₂] (26)。 除此之外，配合物 18 與偶氮苯反應得到雙核配合物 [{Yb(L²)₂}₂(μ-η²:η²-PhNNPh)] (27)， 而 20 與偶氮苯的反應可得單核配合物 [Yb(L³)₂(η²-PhNNPh)･PhMe] (28)。 配合物 22 與二硫化碳的反應得出不對稱偶合配合物 [(L⁵)₂Sm(μ-η³:η²-S₂CSCS)Sm(L⁵)₂] (29)。 / 第四章敍述由胍基配體 L¹ 所衍生的一系列三價鑭系金屬配合物 [Ln(L¹)₃] [Ln = Ce (30), Pr (31), Gd (32), Tb (33), Ho (34), Er (35), Tm (36)] 的合成及其結構。 通過相對應的鑭系金屬三氯化物與 1 反應可得配合物 30-36。 另外， CeCl₃及 LuCl₃與 1 反應亦可合成 [{Ln(L¹)₂(μ-Cl)}₂] [Ln = Ce (37), Lu (38)]。 / 第五章總結了本項研究工作，並對本工作的未來發展作出建議。 / This research work is focused on the coordination chemistry of five closely related guanidinate ligands, namely [(2,6-Me₂C₆H₃N)C(NHPri)(NPri)]⁻ (L¹), [(2,6-Me₂C₆H₃N)C(NHCy)(NCy)]⁻ (L²), [(2,6Me₂C₆H₃N)C{N(SiMe₃)Cy}(NCy)]⁻ (L³), [(2,6Pri₂C₆H₃N)C{N(SiMe₃)₂}(NC₆H₃Pri₂-2,6)]⁻ (L⁴) and [(2,6-Pri₂C₆H₃N)C(NEt₂)(NC₆H₃Pri₂-2,6)]⁻ (L⁵), with divalent chromium and lanthanide metal ions. A series of trivalent lanthanide derivatives of the L¹ ligand were also prepared and structurally characterized in this work. / Chapter 1 gives a brief introduction to the chemistry of metal guanidinate complexes. / Chapter 2 reports on the synthesis, structure and reactivity of chromium(II) complexes derived from the bulky L¹ and L⁴ ligands. Treatment of CrCl₂ with [KL¹･0.5PhMe] (1) afforded the mononuclear Cr(II) bis(guanidinate) complex [Cr(L¹)₂] (3). Reaction of CrCl₂ with [LiL⁴(Et₂O)] (2) resulted in the isolation of ate-complex [Cr(L⁴)(μ-Cl)₂Li(THF)(Et₂O)] (4). Recrystallization of 4 from toluene gave neutral, dimeric [{Cr(L⁴)(μ-Cl)}₂] (5). The reaction chemistry of the Cr(II) complex 3 and 4 was studied. Treatment of 3 with I₂, PhEEPh (E = S, Se, Te), 1-AdN₃ (1-Ad = 1-adamantyl) gave the corresponding mixed-ligand Cr(III) complexes, namely [Cr(L¹)₂I] (6) and [Cr(L¹)₂(EPh)] [E = S (7), Se (8), Te (9)] and Cr(IV) complex [Cr(L¹)₂{N(1-Ad)}] (10). Besides, the reaction of 4 with NaOMe resulted in the isolation of the Cr(II) methoxide-guanidinate complex [{Cr(L⁴)(μ-OMe)}₂] (11). / Chapter 3 deals with the synthesis, structure and reactivity of lanthanide(II) complexes supported by the L¹, L², L³ and L⁵ ligands. Lanthanide(II) guanidinate complexes were prepared by the reactions of an appropriate lanthanide diiodide with the corresponding potassium guanidinate complexes [KL¹･0.5PhMe] (1), [KL²(THF)₀.₅]n (12), KL³ (13) and [KL⁵(THF)₂] (14). Reaction of EuI₂(THF)₂ with 1 gave the homoleptic complex [{Eu(L¹)(μ-L¹)}₂] (15). Metathesis reactions of LnI₂(THF)₂ (Ln = Yb, Eu) with 12 and 13 led to the isolation of [{Ln(L²)(μ-L²)}₂･nC₆H₁₄] [Ln = Eu, n = 2 (16); Ln = Yb, n = 0 (17)], [Yb(L²)₂(THF)₂] (18) and [Ln(L³)₂(THF)₂･0.25C₆H₁₄] [Ln = Eu (19), Yb (20)]. Direct reaction of SmI₂(THF)₂ with 13 yielded the iodide bridged Sm(II) complex [{Sm(L³)(μ-I)(THF)}₂] (21), whilst reaction of SmI₂(THF)₂ with 14 gave homoleptic [Sm(L⁵)₂] (22). The reaction chemistry of 15, 18, 20 and 22 as reducing agents was examined. Oxidation of 15 with I₂ afforded the Eu(III) complex [{Eu(L¹)₂(μ-I)}₂] (23). Reactions of 18 with PhEEPh (E = S, Se) gave the corresponding Yb(III) chalcogenide complexes [{Yb(L²)₂(μ-EPh)}₂] [E = S (24), Se (25)], whilst treatment of 18 with CuCl led to the isolation of [{Yb(L²)₂(μ-Cl)}₂] (26). Besides, addition of complex 18 to PhNNPh yielded binuclear [{Yb(L²)₂}₂(μ-η²:η²-PhNNPh)] (27), whereas treatment of 20 with PhNNPh resulted in the isolation of mononuclear [Yb(L³)₂(η²-PhNNPh)･PhMe] (28). Addition of CS₂ to 22 gave the unsymmetrical coupling product [(L⁵)₂Sm(μ-η³:η²S₂CSCS)Sm(L⁵)₂] (29). / Chapter 4 describes the preparation and structural characterization of lanthanide(III) complexes derived from L¹. A series of homoleptic lanthanide(III) tris(guanidinate) complexes [Ln(L¹)₃] [Ln = Ce (30), Pr (31), Gd (32), Tb (33), Ho (34), Er (35), Tm (36)] were prepared by the reactions of an appropriate LnCl₃ with three molar equivalents of 1. Treatment of CeCl₃ and LuCl₃ with two equivalents of 1 gave the corresponding chloride bridged guanidinate complexes [{Ln(L¹)₂(μ-Cl)}₂] [Ln = Ce (37), Lu (38)]. / Chapter 5 summarizes the findings of this study. A short description on the future prospect of this work will also be given. / 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. / Detailed summary in vernacular field only. / Au, Chi Wai. / Thesis (Ph.D.) Chinese University of Hong Kong, 2014. / Includes bibliographical references. / Abstracts also in Chinese.

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