Thesis (Ph. D.)--University of North Texas, May, 2007. / Title from title page display. Includes bibliographical references.

Thesis (Ph. D.)--Dept. of Chemistry and School of Computing and Engineering. University of Missouri--Kansas City, 2005. / "A dissertation in chemistry and computer networking." Advisor: James R. Durig. Typescript. Vita. Description based on contents viewed Nov. 21, 2007; title from "catalog record" of the print edition. Includes bibliographical references (leaves 415-424). Online version of the print edition.

A series of computational studies were carried out on Group 14 (C, Si and Ge) elements in organometallic and biological compounds. Theoretical studies on classical and H-bridged A3H3+ (A=C, Si and Ge) as p ligands with different organometallic fragments at B3LYP and B3P86 level reveal a reverse charge transfer from ligand to metal in Si and Ge complexes whereas in C complexes there is a small charge transfer from metal to ligand. The H-bridged complexes are more stable than the complexes based on Si3H3+ and Ge3H3+ ligands with terminal hydrogens. The stability of the bridged systems increases from Si to Ge. Corrective scale factors for computed harmonic CºO vibrational frequencies for 31 organometallic complexes have been determined at the HF and B3LYP levels. The scaled B3LYP frequencies exhibit a greater reliability than do HF frequencies. Experimental data have shown that Si/Ge-substituted decapeptides are advantageous over their C analog in vitro and in vivo studies in modern hormone therapy. A computational investigation was carried out on the synthesized decapeptides focusing on position 5 containing Si and Ge. The results have shown that there are some differences in C, Si and Ge-containing analogs. However, further investigations are needed to elucidate the observed advantages of Si/Ge over C analogs.

Wu, Nip Po. / Thesis (M.Phil.)--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 also Chinese.

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

The marriage of synthetic chemistry to materials science has been well documented in the last decade. The design, synthesis, and utilization of chemical precursors in the MOCVD of electronic materials in particular has received a lot of attention in both academic and industrial circles. The maintenance of this symbiotic relationship is pursued in this work in the hope of discovering chemical forerunners for high-dielectric metal oxide materials. Specifically, it is of interest to isolate chemical precursors for ZTT, a recent entry into the field of high-k composites. The primary theme of this dissertation is the exploration of the design and synthesis of molecular precursors that possess more than one of the cations found in the final ZTT film. The approach taken to obtain such precursors, referred to in this work as same-source precursors, is to investigate the implementation of the anionic stannylamine ligand, -N(SnMe3)2 in the preparation of heterometallic coordination complexes. The ultimate goal is to procure volatile, low molecular weight compounds that possess more than one of the metals found in ZTT (tin, titanium, and/or zirconium). The reason for choosing stannylamine ligands is two-fold. First, as was alluded to above, such ligands might provide convenient access to heterometallic complexes possessing tin as one of the metal constituents. Second, since the coordination chemistry of stannyl amines is relatively unexplored compared to alkyl- and silylamine ligands, it is important from a fundamental standpoint to investigate the synthetic utility of this ligand type. With this motivation in mind, the results reported here accomplishe two major objectives: 1) the synthesis and characterization of a variety of metal complexes coordinated by stannylamines and 2) the design, synthesis, and utilization of heterometallic precursors for use in the MOCVD of ZTT. Thus, in the course of a synthetic investigation towards the goal of same-source ZTT precursors for use in MOCVD processes, a number of metal coordination complexes possessing stannylamine ligands have been synthesized and fully characterized. Consequently, the library of known compounds containing these ligands has been significantly expanded and a novel route to volatile, heterobimetallic aminoalkoxide species has been developed.

Thesis (Ph.D.)--McMaster University, 2006. / Supervisor: William J. Leigh. Includes bibliographical references (leaves 236-246).

Thesis (Ph. D.)--Chemistry and Biochemistry, Georgia Institute of Technology, 2005. / William S. Rees, Jr., Committee Chair ; E. Kent Barefield, Committee Member ; Angus P. Wilkinson, Committee Member ; Z. John Zhang, Committee Member ; Dennis W. Hess, Committee Member. Includes bibliographical references.

This thesis focuses on the chemical concept of conjugation, i.e., electron delocalization, and the effect it has on electronic and optical properties of molecules. The emphasis is on electron delocalization across a saturated σ-bonded segment, and in our studies these segments are either inserted between π-conjugated moieties or joined together to form longer chains. The electronic and optical properties of these compounds are probed and compared to those of traditionally π-conjugated compounds. The investigations utilize a combination of qualitative chemical bonding theories, quantum chemical calculations, chemical syntheses and different spectroscopic methods. Herein, it is revealed that a saturated σ-bonded segment inserted between two π-systems can have optical and electronic properties similar to a cross-conjugated compound when substituents with heavy Group 14 elements (Si, Ge or Sn) are attached to the central atom. We coined the terminology cross-hyperconjugation for this interaction, and have shown it by both computational and spectroscopic means. This similarity is also found in cyclic compounds, for example in the 1,4-disilacyclohexa-2,5-dienes, as we reveal that there is a cyclic aspect of cross-hyperconjugation. Cross-hyperconjugation can further also be found in smaller rings such as siloles and cyclopentadienes, and we show on the similarities between these and their cross-π-conjugated analogues, the fulvenes. Here, this concept is combined with that of excited state aromaticity and the electronic properties of these systems are rationalized in terms of “aromatic chameleon” effects. We show that the optical properties of these systems can be rationally tuned and predicted through the choice of substituents and knowledge about the aromaticity rules in both ground and excited states. We computationally examine the relation between conjugation and conductance and reveal that oligomers of 1,4-disilacyclohexa-2,5-dienes and related analogues can display molecular cord properties. The conductance through several σ-conjugated silicon compounds were also examined and show that mixed silicon and carbon bicyclo[2.2.2]octane compounds do not provide significant benefits over the open-chain oligosilanes. However, cyclohexasilanes, a synthetic precursor to the bicyclic compounds, displayed conformer-dependent electronic structure variations that were not seen for cyclohexanes. This allowed for computational design of a mechanically activated conductance switch.

Thesis (Ph. D.)--University of Missouri-Columbia, 2007. / The entire dissertation/thesis text is included in the research.pdf file; the official abstract appears in the short.pdf file (which also appears in the research.pdf); a non-technical general description, or public abstract, appears in the public.pdf file. Title from title screen of research.pdf file (viewed on January 30, 2008) Vita. Includes bibliographical references.