Cheuk Wai So. / "June 2003." / Thesis (Ph.D.)--Chinese University of Hong Kong, 2003. / Includes bibliographical references. / 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. / Abstracts in English and Chinese.

Graduate / 0485

Graduate / 0485

Graduate / 0485

Graduate / 0485

Thesis (M.S.)--Oregon State University, 2005. / Printout. Includes bibliographical references (leaves 69-71). Also available online.

<p> 1,1-Bis(4-(trifluoromethyl)phenyl)germacyclobutane and 1,1-bis(3,5-bis(trifluoromethyl)phenyl)germacyclobutane have been prepared, and their photochemistry studied by steady state and nanosecond laser flash photolysis (NLFP) techniques. Photolysis of the two compounds in the presence of methanol leads to the formation of products resulting from reaction of the alcohol with two germanium-containing reactive intermediates, the germenes and germylenes.</p> <p> The reactivities of the two germenes with nucleophiles such as alcohols, carboxylic acids, and amines have been examined by NLFP techniques, and the results are compared to analogous data for 1,1-diphenylgermene and 1,1-diphenylsilene. Germene reactivity is shown to increase with increasing electron-withdrawing power of the substituents, consistent with a mechanism initiated by nucleophilic attack at germanium. The increased electrophilicity of the substituted 1,1-diarylgermenes results in kinetic behavior indistinguishable from that of 1,1-diphenylsilene, indicating that germenes and silenes form a mechanistic continuum in their reactions with nucleophiles.</p> / Thesis / Master of Science (MSc)

Thesis (MSc)--Stellenbosch University, 2002. / ENGLISH ABSTRACT: There is limited experimental and computational information available on the structures of compounds of the form R2GeX2, where X is a halogen and R an alkyl group. Gas phase electron diffraction studies of the dihalo(dimethyl)germanes (R=Me)consistently give C-Ge-C angles in the range of 120-125°, about 10° larger than the corresponding C-C-C angles in the 2,2-dihalopropanes. However, in dimethylgermane, where the halogen atoms are substituted by hydrogen, the value of the C-Ge-C is very similar to the corresponding C-C-C angle in propane and deviates little from the tetrahedral value of 109.47°. The unusually large influence of atomic substituents on the value of the valence angles in these compounds introduces a serious challenge to the development of empirical force fields, where the size of an angle is traditionally determined only by the atoms directly involved in the formation of the angle and not by the other substituents attached to the central atom. Unfortunately, the large experimental errors in the gas phase electron diffraction studies and the lack of representative crystalline compounds in the Cambridge Structural Database make it impossible to establish conclusively whether these large valence angles are significant or just statistical anomalies. A systematic ab initio study of a number of compounds of the general form Me2AX2with A=C, Si or Ge and X=H, F, Cl, Br or I has been initiated to verify the experimental results and to try to explain this observed deviation in valence angle in terms of electronic effects and existing theories of structure and bonding. The carbon and silicon analogs of the dimethylated germanes were included in the calculations to ascertain whether the observed effect is an anomaly or merely a periodic trend in the group IVelements. To obtain a clearer overall view, identical calculations were also performed on compounds of the form AHnX4-n,MeAH2X, MeAHX2and Me2AHX,where Aand X have the same meaning as before. The ab initio calculations confirmed that there is in fact a significant increase in the C-A-C angle from A=C to A=Ge in the compounds Me2AX2,although the calculated increase is smaller than the experimentally determined increase by a few degrees. Together with this observed increase in the C-A-C angle there is a corresponding decrease in the X-A-X angle. Calculation of the electron density of three representative compounds revealed a significant difference in electron distribution between the germanium compounds and their carbon analogs, suggesting that the ionicity of the bonds and the electronegativity of the substituents may playa role in the size of the C-A-C angle in compounds of this form. This is supported by a statistical analysis of compounds in the Cambridge Structural Database containing a C2GeYZ fragment, where Y and Z may be any elements except carbon, which showed that the average C-Ge-C angle in compounds where Y and Z are electronegative is approximately 7° larger than in compounds where Y and Z are electropositive. The qualitative trends in the C-A-C and X-A-X angles have also been discussed in terms of three different bonding models. To verify the results of the ab initio calculations experimentally, a representative compound, dichlorobis(phenethyl)germane, has been synthesized and its crystal structure determined by X-ray diffraction. The C-Ge-C angle was found to be 121.2°, which is in good agreement with both the ab initio and the gas phase electron diffraction results. Furthermore, a force field for halogenated organic carbon, silicon and germanium compounds has also been developed based on the structural and vibrational data obtained from the ab initio calculations. Molecules of the form AHnX4-nand Me2AX2with A=C, Si, Ge and X=H, F, Cl and Br were used in the training set and the bond lengths, bond angles and vibrational frequencies were used to optimize the force field. Calculations performed with the force field reproduce the C-A-C angles to within 1° of the observed values and the reproducibility for the rest of the experimental data is also good. Force fields have been developed for some of the simpler molecules in our training set and where this is the case, the force field parameters have been compared to the previously determined values. / AFRIKAANSE OPSOMMING: Sien volteks vir opsomming

Wu Yuen Sze. / Thesis (M.Phil.)--Chinese University of Hong Kong, 1999. / Includes bibliographical references (leaves 98-107). / Abstracts in English and Chinese. / Table of contents --- p.i / Acknowledgements --- p.iv / Abstract --- p.v / List of compounds --- p.vi / Abbreviations --- p.x / Chapter Chapter 1 --- Synthesis and Structures of Low-valent Group14 Organometallic Compounds --- p.1 / Chapter 1.1 --- General apects of low-valent group 14 compounds --- p.1 / Chapter 1.2 --- Structures of germylenes and stannylenes --- p.3 / Chapter 1.3 --- Tetravalent group 14 Metal amides --- p.7 / Chapter 1.4 --- Objectives --- p.11 / Chapter 1.5 --- Results and Discussion --- p.12 / Chapter 1.5.1 --- Synthesis of germanium(II) compound [Ge{C(C5H4N- 2)C(Ph)N(SiMe3)2}{N(SiMe3)C(Ph)C(SiMe3)(C5H4N- 2)}] (29) --- p.12 / Chapter 1.5.2 --- Synthesis of tin(II) amide [Sn{N(SiMe3)C(Ph)C- (SiMe3)(C5H4N-2)}2] (30) --- p.14 / Chapter 1.5.3 --- Synthesis of tin(IV)(amide)dichloride [Sn{N(SiMe3)C- (Ph)C(SiMe3)(C5H4N-2)}2Cl2] (31) --- p.15 / Chapter 1.5.4 --- Spectroscopic Properties of Compounds 29-31 --- p.16 / Chapter 1.5.5 --- Molecular Structure of [Ge{C(C5H4N-2)C(Ph)N(Si- Me3)2}{N(SiMe3)C(Ph)C(SiMe3)C(C5H4N-2)}] (29) --- p.21 / Chapter 1.5.6 --- Molecular structure of [Sn{N(SiMe3)C(Ph)C(SiMe3)- (C5H4N-2)}2] (30) --- p.25 / Chapter 1.5.7 --- Molecular structure of [Sn{N(SiMe3)C(Ph)C(SiMe3)- (C5H4N-2)}2C12] (31) --- p.28 / Chapter Chapter 2 --- Synthesis and Structure of Group 14 Metal- Chalcogenones --- p.32 / Chapter 2.1 --- Multiple bond between group 14 metals and chalcogens --- p.32 / Chapter 2.2 --- Results and Discussion --- p.39 / Chapter 2.2.1 --- "Synthesis of germane- and stannane-chalcogenones [(RI)(R1.)Ge=E], [E = S 59, Se 60], [(R1)2Sn=S] (61)， [(R1)(R1.)Sn=Se] (62)" --- p.39 / Chapter 2.2.2 --- Spectroscopic properties of compounds 59-62 --- p.41 / Chapter 2.2.3 --- Molecular structure of [{N(SiMe3)C(Ph)C(SiMe3)- (C5H4N-2)}2Sn=S] (61) --- p.46 / Chapter 2.2.4 --- "Molecular structure of [{N(SiMe3)2C(Ph)C(C5H4N-2)}- {N(SiMe3)C(Ph)C(SiMe3)(C5H4N-2)}M=E] [M = Ge, E =S 59，Se 60; M = Sn,E = Se 62]" --- p.52 / Chapter Chapter 3 --- Reactivity of Low-valent Group 14 Organometallics Compounds --- p.59 / Chapter 3.1 --- Introduction --- p.59 / Chapter 3.1.1 --- Lewis-base behavior --- p.60 / Chapter 3.1.2 --- Lewis-acid behavior --- p.63 / Chapter 3.1.3 --- Oxidative-addition (or insertion) reactions --- p.65 / Chapter 3.2 --- Results and Discussion --- p.69 / Chapter 3.2.1 --- Lewis acid base behavior of [Sn(R2)2] (27) --- p.69 / Chapter 3.2.1.1 --- "Reaction of [Sn(R2)2] (27) with group 11 metal derivatives (M = Ag, X = Cl 91,I 92,SCN 93，CN94; M = Cu, X = Cl 95，I 96)-Synthesis of [(R2)2Sn→(μ- MX)]2" --- p.69 / Chapter 3.2.2 --- Oxidative-addition (or insertion) reaction of tin(II) compounds --- p.73 / Chapter 3.2.2.1 --- Reaction of AgNCO with [Sn(R2)2] (27) 一 Synthesis of [(R2)2Sn(NCO)2](97) --- p.73 / Chapter 3 .2.3 --- Spectroscopic properties of compounds 91-97 --- p.74 / Chapter 3.2.4 --- Molecular structure of [{CH(SiMe3)C9H6N-8}2Sn→(μ- AgCl)]2 (91) --- p.80 / Chapter 3.2.5 --- Molecular structure of [{CH(SiMe3)C9H6N-8}2Sn- (NCO)2] (97) --- p.85 / Appendix I / Chapter A. --- Experimental procedures for chapter 1 --- p.87 / Chapter B. --- Experimental procedures for chapter 2 --- p.90 / Chapter C. --- Experimental procedures for chapter 3 --- p.93 / Appendix II / Chapter A. --- References for chapter 1 --- p.98 / Chapter B. --- References for chapter 2 --- p.102 / Chapter C. --- References for chapter 3 --- p.104 / Appendix III / Chapter A. --- General procedures --- p.106 / Chapter B. --- Physical and analytical measurements --- p.106 / Appendix IV / Table A.l. Selected crystallographic data for compounds 29，30，31 --- p.109 / Table A.l. Selected crystallographic data for compounds 59，60，61 --- p.110 / "Table A.l. Selected crystallographic data for compounds 62, 91，97" --- p.111

本論文工作主要包括三部分: (i) 含吡啶基-1-氮雜烯丙基配體的二价鍺氯化物的反應研究； (ii) 含吡啶基-1-氮雜烯丙基配體的一价鍺二聚體的合成及反應研究; (iii) 膦亞胺配體衍生的低价態第十四族金屬復合物及金屬亞乙烯的合成與反應研究。 / 第一章描述含吡啶基-1-氮雜烯丙基配位體的二价鍺氯化物66的反應。化合物66與Na[M(η⁵-C₅H₅)(CO)₃]2DME (M = Mo or W)反應，得到含鍺(II)-金屬單鍵的異核雙金屬鍺亞乙烯化合物76及77。化合物66與環戊二烯鈉反應生成了環戊二烯基取代的鍺烯。作為路易斯鹼，化合物66與大位阻硼烷的反應得到研究。化合物66與B(C₆F₅)₃反應，得到路易斯酸-鹼加合物79。此外，化合物66與三价氯化鎵及三价氯化銦進行的配體轉移反應也得到研究。另外，化合物66與水的反應產生[{HNC(Ph)CH(C₅H₄N-2)}GeCl] (82)。 / 第二章描述化合物66的還原化學。二价鍺氯化物66與過量鎂反應得到 [N(SiMe₃)C(Ph)C(SiMe₃) (C₅H₄N-2)Mg(μ-Cl)(THF)]₂ (110)和[C(Ph)C(SiMe₃)(C₅H₄N-2)]₂Ge₂ (111)的混合物。而其與過量金屬鋰反應則得到一价鍺二聚體[C(Ph)C(SiMe₃)(C₅H₄N-2)]₂Ge₂ (111)及[N(SiMe₃)C(Ph)C(SiMe₃) (C₅H₄N-2)]₂Ge₂ (112)。化合物66與等當量石墨鉀反應，主要得到一价鍺二聚體112。化合物112與偶氮苯反應得到鍺聯氨衍生物[PhNGe{N(SiMe₃) C(Ph)C(SiMe₃)(C₅H₄N-2)}]₂₋(113)。化合物112的路易斯鹼性得到研究。化合物112與一當量九羰基二鐵反應生成新型不對稱一价鍺二聚體[{N(SiMe₃)C(Ph)C(SiMe₃)(C₅H₄N-2)(Fe(CO)₄)- Ge-Ge{N(SiMe₃)C(Ph)C(SiMe₃)(C₅H₄N-2)}](114)，而其與兩當量九羰基二鐵反應則得到[{N(SiMe₃)C(Ph)C(SiMe₃)(C₅H₄N-2)Fe(CO)₄)Ge]₂(115)。此外，二聚體112與硫磺進行反應，得到首個鍺二硫代羧酸酐的鍺類似物。 / 第三章介紹從膦亞胺配體衍生的二价態第十四族金屬復合物的合成，描述了由配體Ph₂P(2-CH₂Py)=NSiMe₃ (119)及H₂C(PPh₂=NSiMe₃)₂ (121)衍生的二价鍺及二价錫化合物的合成。此外，本章研究了半穏定配體Ph₂PCH₂(PPh₂=NSiMe₃) (131)的配位化學。化合物131在Bu[superscript n]Li及Bu[superscript n]₂Mg的作用下金屬化分解反應，分別生成膦亞胺鋰化合物[Li{CH(PPh₂)(PPh₂=NSiMe₃)}(THF)₂] (194)及鎂化合物[Mg{CH(PPh₂)(PPh₂=NSiMe₃)}₂] (193)。化合物194與相應的二价金屬氯化物反應得到1,3-二錫環丁烷196和1,3-二鉛環丁烷200。化合物194與二氯化鍺二噁烷配合物的反應得到新型三核雜環化合物195。此外，化合物196與九羰基二鐵反應，得到膦穏定的錫亞乙烯197。 / 第四章為第一至第三章的總結。 / This thesis is focused on three areas: (i) the reactivities of pyridyl-1-azaallyl germanium(II) chloride; (ii) the synthesis and reactivities of pyridyl-1-azaallyl germanium(I) dimer; (iii) the synthesis and reactivities of low-valent main group 14 metal complexes and metallavinylidenes derived from phosphoranoimines. / Chapter 1 describes the reactivities of pyridyl-1-azaallyl germanium(II) chloride [{N(SiMe₃)C(Ph)C(SiMe₃)(C₅H₄N-2)}GeCl] (66). The reaction of 66 with Na[M(η⁵-C₅H₅)(CO)₃]2DME (M = Mo or W) affords heterobimetallic germylenes 76 and 77 which contain a germanium(II)-metal single bond. A Cp-substituted germylene was prepared from the reaction of 66 with sodium cyclopentadienylide. The Lewis base behavior of 66 toward bulky borane was investigated. Treatment of 66 with B(C₆F₅)₃ leads to the formation of a Lewis acid-base adduct 79. Furthermore, the ligand transfer reaction of 66 with GaCl₃ and InCl₃ were studied. In addition, the reaction of 66 with water affords [{HNC(Ph)CH(C₅H₄N-2)}GeCl] (82). / Chapter 2 describes the reduction chemistry of 66. Treatment of 66 with excess magnesium tunings affords a mixture of products [N(SiMe₃)C(Ph)C(SiMe₃)- (C₅H₄N-2)Mg(μ-Cl)(THF)]₂ (110) and [C(Ph)C(SiMe₃)(C₅H₄N-2)]₂Ge₂ (111). The reaction of 66 with an excess of lithium metals leads to a mixture of germanium(I) dimers [C(Ph)C(SiMe₃)(C₅H₄N-2)]₂Ge₂ (111) and [N(SiMe₃)C(Ph)C(SiMe₃)- (C₅H₄N-2)]₂Ge₂ (112). When compound 66 was treated with one equivalent of potassium graphite, compound 112 was obtained as the major product. The reaction of 112 with azobenzene affords the 1,2-digermylene hydrazinide [PhNGe{N(SiMe₃) C(Ph)C(SiMe₃)(C₅H₄N-2)}]₂ (113). The Lewis base behaviour of 112 was studied. Treatment of 112 with one equivalent of diironnonacarbonyl gives a new unsymmetric germanium(I) dimer [{N(SiMe₃)C(Ph)C(SiMe₃)(C₅H₄N-2)(Fe(CO)₄)- Ge-Ge{N(SiMe₃)C(Ph)C(SiMe₃)(C₅H₄N-2)}] (114), while the reaction of 112 with two equivalent of diironnonacarbonyl leads to the formation of [{N(SiMe₃)C- (Ph)C(SiMe₃)(C₅H₄N-2)Fe(CO)₄)Ge]₂ (115). In addition, the reaction of 112 with sulfur affords the first germanium analogue of a dithiocarboxylic acid anhydride. / Chapter 3 deals with the synthesis of group 14 metal(II) complexes supported by iminophosphoranyl ligands. The synthesis of germanium(II) and tin(II) compounds derived from Ph₂P(2-CH₂Py)=NSiMe₃ (119) and H₂C(PPh₂=NSiMe₃)₂ (121) are described. Furthermore, the coordination chemistry of the hemilabile ligand Ph₂PCH₂(PPh₂=NSiMe₃) (131) was investigated. Iminophosphoranyl phosphine 131 undergoes metalation with Bu[superscript n]Li and Bu[superscript n]₂Mg to give the lithium complex [Li{CH(PPh₂)(PPh₂=NSiMe₃)}(THF)₂] (194) and the magnesium complex [Mg{CH- (PPh₂)(PPh₂=NSiMe₃)}₂] (193), respectively. 1,3-distannylcyclobutane 196 and 1,3-diplumbacyclobutane 200 were prepared from the reaction of 194 with the corresponding metal(II) chlorides. The reaction of 194 with GeCl₂(dioxane) leads to a tri-nuclear heterocyclic cage compound 195. In addition, the trapping reaction of 196 with diironnonacarbonyl affords the phoshpine-stabilized stannavinylidene 197. / Chapter 4 describes the conclusion of the first three chapters. / 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. / Chiu, Wang Kin. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2013. / Includes bibliographical references. / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstracts in also in Chinese. / Tables of Contents --- p.vi / Acknowledgments --- p.i / Abstract --- p.ii / 摘要 --- p.iv / List of Compounds Synthesized --- p.xiv / Abbreviations --- p.xvi / Chapter Chapter 1 --- Reactivity of Pyridyl-1-azaallyl Germanium(II) Chloride / Chapter 1.1 --- Introduction --- p.1 / Chapter 1.1.1 --- Reactivity Study of Heteroleptic Organogermanium(II) Chlorides --- p.1 / Chapter 1.1.2 --- Synthesis and Structure of Pyridyl-1-azaallyl Germanium(II) Chloride --- p.13 / Chapter 1.1.3 --- Objectives --- p.15 / Chapter 1.2 --- Results and Discussion --- p.18 / Chapter 1.2.1.1 --- Synthesis of Metallo-germylenes from Pyridy1-1-azaallyl Germanium (II) chloride --- p.19 / Chapter 1.2.1.2 --- Spectroscopic Properties of [{N(SiMe₃)C(Ph)C(SiMe₃)- (C₅H₄N-2)}Ge-M(η⁵-C₅H₅)(CO)₃] (M = Mo (76), W (77) --- p.19 / Chapter 1.2.1.3 --- Molecular Structures of [{N(SiMe₃)C(Ph)C(SiMe₃) (C₅H₄N-2)}Ge-M(η⁵-C₅H₅)(CO)₃] (M = Mo (76), W (77)) --- p.20 / Chapter 1.2.2.1 --- Synthesis of Heteroleptic Germylene [{N(SiMe₃)C(Ph)C- (SiMe₃)(C₅H₄N-2)}Ge(η¹-C₅H₅)] (78) --- p.25 / Chapter 1.2.2.2 --- Spectroscopic Properties of [{N(SiMe₃)C(Ph)C(SiMe₃)- (C₅H₄N-2)}Geη¹-C₅H₅)] (78) --- p.25 / Chapter 1.2.2.3 --- Molecular Structures of [{N(SiMe₃)C(Ph)C(SiMe₃)- (C₅H₄N-2)}Ge(η¹-C₅H₅)] (78) --- p.26 / Chapter 1.2.3.1 --- Synthesis of Germanium(II)-Borane Adduct Adduct Adduct [{N(SiMe₃)C(Ph)C(SiMe₃)(C₅H₄N-2)}Ge(Cl)→(B(C₆H₅)₃)] (79) --- p.29 / Chapter 1.2.3.2 --- Spectroscopic Properties of Germanium(II)-Borane Adduct Adduct [{N(SiMe₃)C(Ph)C(SiMe₃)(C₅H₄N-2)}Ge(Cl)→(B(C₆H₅)₃)](79) --- p.29 / Chapter 1.2.3.3 --- Molecular Structures of Germanium(II)-Borane Adduct Adduct [{N(SiMe₃)C(Ph)C(SiMe₃)(C₅H₄N-2)}Ge(Cl)→(B(C₆H₅)₃)](79) --- p.30 / Chapter 1.2.4.1 --- Synthesis of Pyridyl-1-azaallyl Group 13 Metal Complexes from the Ligand Transfer Reaction between Pyridyl-1-azaallyl Germanium(II) Chloride and Group 13 Metal Halides --- p.34 / Chapter 1.2.4.2 --- Spectroscopic Properties of [{N(SiMe₃)C(Ph)C(SiMe₃)- (C₅H₄N-2)}GaCl₂] (80) and [{N(SiMe₃)C(Ph)C(SiMe₃)- (C₅H₄N-2)}₂InCl] (81) --- p.35 / Chapter 1.2.4.3 --- Molecular Structures of [{N(SiMe₃)C(Ph)C(SiMe₃)- (C₅H₄N-2)}GaCl₂] (80) and [{N(SiMe₃)C(Ph)C(SiMe₃)- (C₅H₄N-2)}₂InCl] (81) --- p.36 / Chapter 1.2.5.1 --- Hydrolysis of Pyridyl-1-azaallyl Germanium(II) Chloride with Water --- p.40 / Chapter 1.2.5.2 --- Spectroscopic Properties of [{HNC(Ph)CH(C₅H₄N-2)}GeCl] (82) --- p.40 / Chapter 1.2.5.3 --- Molecular Structure of [{HNC(Ph)CH(C₅H₄N-2)}GeCl] (82) --- p.41 / Chapter 1.3 --- Experimental for Chapter 1 --- p.43 / Chapter 1.4 --- References for Chapter 1 --- p.49 / Chapter Chapter 2 --- Synthesis and Reactivity Study of Pyridyl-1-azaallyl Germanium(I) Dimer / Chapter 2.1 --- Introduction --- p.55 / Chapter 2.1.1 --- General Aspects of Digermynes and Germanium(I) Dimers Supported by Bulky Ligands --- p.55 / Chapter 2.1.2 --- Objectives --- p.67 / Chapter 2.2 --- Results and Discussion --- p.69 / Chapter 2.2.1.1 --- Reduction of Pyridyl-1-azaallyl Germanium(II) Chloride:Synthesis of Germanium(I) Dimers [C(Ph)C(SiMe₃)- (C₅H₄N-2)]₂Ge₂ (111) and [N(SiMe₃)C(Ph)C(SiMe₃)- (C₅H₄N-2)]₂Ge₂ (112) --- p.69 / Chapter 2.2.1.2 --- Spectroscopic Properties of [N(SiMe₃)C(Ph)C(SiMe₃)- (C₅H₄N-2)Mg(μ-Cl)(THF)]₂ (110), [C(Ph)C(SiMe₃)- (C₅H₄N-2)]₂Ge₂ (111) and [N(SiMe₃)C(Ph)C(SiMe₃)- (C₅H₄N-2)]₂Ge₂ (112) --- p.71 / Chapter 2.2.1.3 --- Molecular Structures of [N(SiMe₃)C(Ph)C(SiMe₃)- (C₅H₄N-2)Mg(μ-Cl)(THF)]₂(110), [C(Ph)C(SiMe₃)- (C₅H₄N-2)]₂Ge₂ (111) and [N(SiMe₃)C(Ph)C(SiMe₃)- (C₅H₄N-2)]₂Ge₂ (112) --- p.72 / Chapter 2.2.2.1 --- Synthesis of [PhNGe{N(SiMe₃)C(Ph)C(SiMe₃)(C₅H₄N-2)}]₂ (113) --- p.80 / Chapter 2.2.2.2 --- Spectroscopic Properties of [PhNGe{N(SiMe₃)C(Ph)C(SiMe₃)(C₅H₄N-2)}]₂ (113) --- p.80 / Chapter 2.2.2.3 --- Molecular Structure of [PhNGe{N(SiMe₃)C(Ph)C(SiMe₃)(C₅H₄N-2)}]₂ (113) --- p.80 / Chapter 2.2.3.1 --- Synthesis of [{N(SiMe₃)C(Ph)C(SiMe₃)(C₅H₄N-2)(Fe(CO)4)- Ge-Ge{N(SiMe₃)C(Ph)C(SiMe₃)(C₅H₄N-2)}] (114) and [{N(SiMe₃)C(Ph)C(SiMe₃)(C₅H₄N-2)(Fe(CO)4)Ge]₂ (115) --- p.84 / Chapter 2.2.3.2 --- Spectroscopic Properties of [{N(SiMe₃)C(Ph)C(SiMe₃)(C₅H₄N-2)(Fe(CO)₄)- Ge-Ge{N(SiMe₃)C(Ph)C(SiMe₃)(C₅H₄N-2)}](114) and [{N(SiMe₃)C(Ph)C(SiMe₃)(C₅H₄N-2)(Fe(CO)₄)Ge]₂ (115) --- p.86 / Chapter 2.2.3.3 --- Molecular Structures of [{N(SiMe₃)C(Ph)C(SiMe₃)(C₅H₄N-2)(Fe(CO)₄)- Ge-Ge{N(SiMe₃)C(Ph)C(SiMe₃)(C₅H₄N-2)}](114) and [{N(SiMe₃)C(Ph)C(SiMe₃)(C₅H₄N-2)(Fe(CO)₄)Ge]₂ (115) --- p.87 / Chapter 2.2.4.1 --- Synthesis of the First Germanium Analogue of a Dithiocarboxylic Acid Anhydride: [Ge(S){N(SiMe₃)C(Ph)C(SiMe₃)(C₅H₄N-2)}]₂S (117) --- p.90 / Chapter 2.2.4.2 --- Spectroscopic Properties of [Ge(S){N(SiMe₃)C(Ph)C(SiMe₃)(C₅H₄N-2)}]₂S (117) --- p.91 / Chapter 2.2.4.3 --- Molecular Structure of [Ge(S){N(SiMe₃)C(Ph)C(SiMe₃)(C₅H₄N-2)}]₂S (117) --- p.92 / Chapter 2.3 --- Experimental for Chapter 2 --- p.95 / Chapter 2.4 --- References for Chapter 2 --- p.103 / Chapter Chapter 3 --- Synthesis and Characterization of Iminophosphoranyl Methanide Metal Complexes and Group 14 Metallavinylidenes / Chapter 3.1 --- Introduction --- p.109 / Chapter 3.1.1 --- A General Review of Phosphoranoimine Ligands --- p.109 / Chapter 3.1.2 --- A General Review of Group 14 Metal Complexes Containing Phosphoranoimine Ligands --- p.117 / Chapter 3.1.3 --- Objectives --- p.124 / Chapter 3.2 --- Results and Discussion --- p.126 / Chapter 3.2.1.1 --- Synthesis of Heteroleptic Chlorogermylene [{(C₅H₄N-2)C(SiMe₃)P(Ph)₂N(SiMe₃)}GeCl (189) and Chlorostannylene [{(C₅H₄N-2)C (SiMe₃)P(Ph)₂N(SiMe₃)}SnCl] (190) --- p.126 / Chapter 3.2.1.2 --- Spectroscopic Properties of [{(C₅H₄N-2)C(SiMe₃)P(Ph)₂N(SiMe₃)}GeCl (189) and Chlorostannylene [{(C₅H₄N-2)C (SiMe₃)P(Ph)₂N(SiMe₃)}SnCl] (190) --- p.127 / Chapter 3.2.1.3 --- Molecular Structures of [{(C₅H₄N-2)C(SiMe₃)P(Ph)₂N(SiMe₃)}GeCl (189) and Chlorostannylene [{(C₅H₄N-2)C (SiMe₃)P(Ph)₂N(SiMe₃)}SnCl] (190) --- p.128 / Chapter 3.2.2.1 --- Synthesis of Bis(iminophosphoranyl) Germanium(II) Compounds [{H₂C(PPh₂=NSiMe₃)₂}(GeCl₂)] (191) and [HC(PPh₂=N- SiMe₃)₂Ge(η¹-C₅H₅)] (192) --- p.132 / Chapter 3.2.2.2 --- Spectroscopic Properties of [{H₂C(PPh₂=NSiMe₃)₂}(GeCl₂)] (191) and [HC(PPh₂=NSiMe₃)₂Ge(η¹-C₅H₅)] (192) --- p.133 / Chapter 3.2.2.3 --- Molecular Structures of [{H₂C(PPh₂=NSiMe₃)₂}(GeCl₂)] (191) and [HC(PPh₂=NSiMe₃)₂Ge(η¹-C₅H₅)] (192) --- p.134 / Chapter 3.2.3.1 --- Synthesis of Magnesium and Lithium Methanide Complexes [Mg{CH(PPh₂)(PPh₂=NSiMe₃)}₂] (193) and [Li{CH(PPh₂)- (PPh₂=NSiMe₃)}(THF)₂] (194) --- p.139 / Chapter 3.2.3.2 --- Spectroscopic Properties of [Mg{CH(PPh₂)(PPh₂=NSiMe₃)}₂] (193) and [Li{CH(PPh₂)- (PPh₂=NSiMe₃)}(THF)₂] (194) --- p.140 / Chapter 3.2.3.3 --- Molecular Structures of [Mg{CH(PPh₂)(PPh₂=NSiMe₃)}₂] (193)and [Li{CH(PPh₂)- (PPh₂=NSiMe₃)}(THF)₂] (194) --- p.141 / Chapter 3.2.4.1 --- Synthesis of Phosphine-Stabilized Germavinylidene [{(PPh₂=NSiMe₃)(PPh₂)C=Ge:}{(PPh₂=NSiMe₃)(PPh₂)C}₂Ge→Ge:] (195) --- p.145 / Chapter 3.2.4.2 --- Spectroscopic Properties of [{(PPh₂=NSiMe₃)(PPh₂)C=Ge:}{(PPh₂=NSiMe₃)(PPh₂)C}₂Ge→Ge:] (195) --- p.146 / Chapter 3.2.4.3 --- Molecular Structure of [{(PPh₂=NSiMe₃)(PPh₂)C=Ge:}{(PPh₂=NSiMe₃)(PPh₂)C}₂Ge→Ge:] (195) --- p.146 / Chapter 3.2.5.1 --- Synthesis of Phosphine-Stabilized Stannavinylidene [{(PPh₂=NSiMe₃)(PPh₂)C=Sn:}{(PPh₂=NSiMe₃)(PPh₂)C=Sn→ Fe(CO)₄}] (197) --- p.151 / Chapter 3.2.5.2 --- Spectroscopic Properties of [Sn{{471}²-C(PPh₂=NSiMe₃)(PPh₂)}](196) and [{(PPh₂=NSiMe₃)(PPh₂)C=Sn:}{(PPh₂=NSiMe₃)(PPh₂)C=Sn→Fe(CO)₄}] (197) --- p.152 / Chapter 3.2.5.3 --- Molecular Structures of [Sn{{471}²-C(PPh₂=NSiMe₃)(PPh₂)}] (196) and [{(PPh₂=NSiMe₃)(PPh₂)C=Sn:}{(PPh₂=NSiMe₃)(PPh₂)C=Sn→Fe(CO)₄}] (197) --- p.157 / Chapter 3.2.6.1 --- Synthesis of 1, 3-diplumbacyclobutane [Pb{{471}²-C(PPh₂=NSiMe₃)- (PPh₂)}]₂ (200) derived from iminophosphoranyl phosphine --- p.163 / Chapter 3.2.6.2 --- Spectroscopic Properties of [Pb{{471}²-C(PPh₂=NSiMe₃)- (PPh₂)}]₂ (200) --- p.164 / Chapter 3.2.6.3 --- Molecular Structure of [Pb{{471}²-C(PPh₂=NSiMe₃)- (PPh₂)}]₂ (200) --- p.164 / Chapter 3.3 --- Experimental for Chapter 3 --- p.167 / Chapter 3.4 --- References for Chapter 3 --- p.176 / Chapter Chapter 4 --- Conclusion / Chapter 4.1 --- Conclusion --- p.186 / Chapter 4.1.1 --- Reactivity Study of Pyridyl-1-azaallyl Germanium(II) Chloride --- p.186 / Chapter 4.1.2 --- Synthesis and Reactivity Study of Pyridyl-1-azaallyl Germanium(I) Dimer --- p.187 / Chapter 4.1.3 --- Synthesis and Characterization of Iminophosphoranyl Methanide Metal Complexes and Group 14 Metallavinylidenes --- p.191 / Chapter 4.2 --- References for Chapter 4 --- p.193 / Chapter Appendix I / Chapter A. --- General Procedures --- p.194 / Chapter B. --- Physical and Analytical Measurements --- p.194 / Chapter Appendix II / Chapter Table A.1. --- Selected Crystallographic Data for Compounds 76-79 --- p.197 / Chapter Table A.2. --- Selected Crystallographic Data for Compounds 80-82 and 110 --- p.198 / Chapter Table A.3. --- Selected Crystallographic Data for Compounds 111-114 --- p.199 / Chapter Table A.4. --- Selected Crystallographic Data for Compounds 117 and 118-191 --- p.200 / Chapter Table A.5. --- Selected Crystallographic Data for Compounds 192-195 --- p.201 / Chapter Table A.6. --- Selected Crystallographic Data for Compounds 196-197 and 200 --- p.202