In recent years, there has been considerable interest in media which exhibit significant non-linear physical properties. The non-linear optical response of many materials has attracted a great deal of attention from the telecommunications industry owing to their possible use for signal processing applications. Also, applications such as thermal imaging depend ultimately upon the proficient operation of the active material within the device structure. Traditionally, inorganic materials such as lithium niobate and strontium barium niobate have been used for non-linear optics and infra-red detection. However, the last decade or so has exposed the potentially high efficiency offered by organic materials which, coupled to the ability to engineer their physical properties by subtle modifications at the molecular level, suggests an exciting and productive future. In order to maintain compatibility with existing integrated optics and display technologies, it is often useful to process the active compound in thin film form. The stringent symmetry requirements imposed upon the molecules and their organisation in the macroscopic structure necessitates the existence of non-centrosymmetric molecular structures for second-order non-linear applications such as those mentioned above. The Langmuir-Blodgett deposition technique enables such assemblies to be constructed by the sequential transfer of organic monomolecular layers from a liquid-air interface onto a solid substrate. The precise control of film thickness and molecular architecture afforded by the technique allow polar multilayer structures to be produced which possess the properties required for highly efficient second-order non-linear physical operation. This thesis describes the development of a series of novel organo-metallic complexes which possess the necessary molecular properties for LB deposition in addition to those required for the observation of a large non-linear response. The complexes offer substantially improved thermal stability over other LB materials, and are thus appealing to the industrial device engineer. Their physical properties have been systematically studied and related to their detailed molecular structure. In particular, optical second-harmonic generation studies have shown that they possess high molecular coefficients and have provided a launching stage for further development. Their high pyroelectric response has attracted much enthusiasm from both industry and academia because of their potential commercial exploitation in thermal imaging devices.

The B3LYP density functional has been used to calculate properties of organometallic complexes of Co(CO)3 and ReBr(CO)3, with the chelating ligand 2,3-bisphosphinomaleic anhydride, in 19- and 18-electron forms. The SBKJC-21G effective core potential and associated basis set was used for metals (Co/Re) and the 6-31G* basis set was used for all other elements. The differences of bond angles, bond distances, natural atomic charges and IR vibrational frequencies were compared with the available experimental parameters. The differences between the 19- and 18-electron systems have been analyzed. The results reveal that the 19th electron is mostly distributed over the ligand of 2,3-bisphosphinomaleic anhydride, although partially localized onto the metal fragment in 1 and 2*. Two different methods, IR-frequencies and natural atomic charges, were used to determine the value of δ. Present computed values of δ are compared with available experimental values, and predictions are made for unknown complexes.

N-Heterocyclic Carbenes (NHC) present a viable alternative to traditional phosphine ligands in a variety of organometallic mediated catalytic reactions. Singlet ground-state carbenes are stabilized by the push-pull presence of two adjacent nitrogen atoms in an imidizolium 5-membered ring, allowing neutral electron donor properties. The ability to synthesize a variety of NHC ligands with differing steric and electronic properties is possible by changing the sustiuents on the nitrogen atoms of the imidizolium. Tunable characteristics and enhanced chemical and thermal stability give NHC’s an advantage over phosphines in many catalytic systems. This dissertation focuses on the use N-Hetercyclic Carbenes in a variety of organometallic complexes. The synthesis of NHC complexes with a variety of transition metals is described. The transition metals complexed with NHC’s include palladium, iridium, nickel and ruthenium. The catalytic activity of the metal-NHC complexes is investigated as well.

Thesis advisor: James P. Morken / This dissertation details recent developments in palladium catalyzed carbon-carbon bond formation reactions with two areas of focus: the palladium catalyzed branched and enantioselective allyl-allyl cross-coupling, and the palladium catalyzed carbonylative conjugate addition. Allyl-allyl cross-coupling presents an opportunity to synthesize 1,5-dienes, a scaffold that resembles subunits of terpenes, a critical building block in nature. Chapter I provides an overview of the developments in the allyl-allyl cross-coupling area. Chapter II, III, and IV detail strategies to construct complex substituted asymmetric 1,5-dienes through branched selective and enantioselective allyl-allyl cross-coupling. In chapter V, the palladium catalyzed carbonylative conjugate addition is discussed. This method enables the synthesis of 1,4-dicarbonyl compounds in an atom economical and environmentally friendly fashion, and provides a direct access to five membered heterocycles, a valuable class of chemicals in medicine. / Thesis (PhD) — Boston College, 2014. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Fong Ching-yee. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2002. / Includes bibliographical references (leaves 72-76). / Abstracts in English and Chinese. / ABSTRACT (English Version) --- p.iii / ABSTRACT (Chinese Version) --- p.v / ACKNOWLEGEMENT --- p.vi / TABLE OF CONTENTS --- p.vii / LIST OF TABLES --- p.ix / LIST OF FIGURES --- p.xi / LIST OF APPENDICES --- p.xiii / Chapter CHAPTER ONE --- Introduction / Chapter 1.1 --- Importance and Recent Development in Metalloporphyrin --- p.1 / Chapter 1.2 --- Structure of Metalloporphyrin --- p.2 / Chapter 1.3 --- General Properties of Metalloporphyrin --- p.4 / Chapter 1.4 --- Linkage Patterns of Metalloporphyrin Polymers --- p.7 / Chapter 1.5 --- Reasons for Studying Co-Por-Au Polymer --- p.10 / Chapter CHAPTER TWO --- Cobalt Porphyrin Gold (Co-Por-Au) Polymer Model / Chapter 2.1 --- Synthetic Scheme --- p.13 / Chapter 2.2 --- Experimental Results and Related Properties --- p.14 / Chapter 2.3 --- The Structure of Co-Por-Au Polymer --- p.18 / Chapter CHAPTER THREE --- Structure Characterization of Co-Por-Au Polymer by DFT Method / Chapter 3.1 --- Quantum Chemical Calculations --- p.21 / Chapter 3.2 --- Density Functional Theory --- p.22 / Chapter 3.3 --- Computational Details --- p.24 / Chapter 3.4 --- Justification for using Gaussian 98 and VASP --- p.27 / Chapter 3.5 --- Results and Discussions --- p.30 / Chapter 3.5.1 --- Monomers of TPHP and TPCNP --- p.30 / Chapter 3.5.1.1 --- The Geometry of the Monomer Structures of TPhP and TPCNP --- p.30 / Chapter 3.5.1.2 --- The Axial Coordination Mode of Monomer in TPhP and TPCNP --- p.34 / Chapter 3.5.1.3 --- Comparison between Hybrid DFT and Pure DFT method --- p.38 / Chapter 3.5.1.4 --- Comparison with Other Porphyrin System --- p.40 / Chapter 3.5.1.5 --- Summary --- p.43 / Chapter 3.5.2 --- Polymers of TPhP and TPcnP --- p.44 / Chapter 3.5.2.1 --- (μ-pyrazine)(octaethylporphyrinato)iron(II) {[Fe(OEP)pyz]}n --- p.44 / Chapter 3.5.2.2 --- Energetic Comparison of TPHP and TPCNP with Different Axial Coordination Modes --- p.46 / Chapter 3.5.2.3 --- Geometry of the Repeating Units in the Polymer of TPhP and TPCNP --- p.48 / Chapter 3.5.2.4 --- Comparison with Other Porphyrin System --- p.52 / Chapter 3.5.2.5 --- The Electronic Structures of TPHP and TPCNP --- p.55 / Chapter 3.5.2.6 --- Summary --- p.58 / Chapter CHAPTER FOUR --- Conclusion --- p.59 / APPENDIX I-III --- p.61 / REFERENCES --- p.72

Wong, Hung Kit. / 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 in Chinese.

本論文論述的內容主要包括兩部分：(i) 從兩種新型磷亞硫配位體CH₂(iPr₂P=S)(C₉H₆N-2) (111) 和 {CH₂([superscript i]Pr₂P)}₂(C₄H₂N₂-2,3) (113) 衍生出的主族金屬、過渡金屬以及鑭系金屬複合物的合成及結構表徵，(ii) 從不同的磷亞胺配位體CH₂(PPh₂=NSiMe₃)₂ (2) 和 CH₂(R₂P=S)(C₉H₆N-2) [R = [superscript i]Pr (110a), R = Ph (110b)] 衍生出的第十四族複合物的合成、結構表徵以及其反應活性的研究。 / 第一章概述以磷亞胺和磷亞硫作為配位體而衍生的主族金屬、過渡金屬以及鑭系金屬復合物。接著描述了新穎的磷亞胺配位體 CH₂(R₂P=NSiMe₃)(C₉H₆N-2) [R = [superscript i]Pr (110a), R = Ph (110b)] 和磷亞硫配位體CH₂([superscript i]Pr₂P=S)(C₉H₆N-2) (111) 和 [{CH₂([superscript i]Pr₂P)}₂C₄H₂N₂-2,3] (113) 的合成方法以及結構表徵。透過111與 [superscript n]BuLi和[superscript n]Bu₂Mg的去質子化反應生成了相應的鋰複合物[Li(Et₂O){CH([superscript i]Pr₂P-S) (C₉H₆N-2)}]₂ (114) 及鎂複合物[Mg{CH(iPr₂P-S)(C₉H₆N-2)}₂] (115)。化合物 114透過與K[superscript t]BuO的金屬轉移反應生成鉀複合物 [K{CH([superscript i]Pr₂P-S)(C₉H₆N-2)}][subscript n] (116) 。透過113與 [superscript n]Bu₂Mg的去質子化反應生成了四聚體的鎂複合物[Mg{CH ([superscript i]Pr₂P=S)}₂C₄H₂N₂-2,3]₄ (118) 。 / 第二章描述由化合物 111 衍生出的第十三族及第十四族複合物的合成及結構表徵。透過111與一倍當量的AlMe₃的去質子化反應生成了相應的鋁複合物[AlMe₂{CH([superscript i]Pr₂P-S)(C₉H₆N-2)}] (153) 。此外，透過111與相應的第十四族二價金屬酰胺進行了脫胺反應生成了第十四族“開盒型的1,3-雙金屬化環丁烷 [M{μ²-C([superscript i]Pr₂P=S)(C₉H₆N-2)}]₂ [M= Sn (155) 及 Pb (156)] 。透過鋰複合物114與兩倍當量的 AlCl₃或GaCl₃進行复分解反應生成了第十三族金屬氯複合物[MCl₂{CH([superscript i]Pr₂P-S)(C₉H₆N-2)}] [M = Al (157) 及 Ga (158)] 。透過鋰複合物114與兩倍當量的 GeCl₄或SnCl₄進行复分解反應則生成了四價鍺氯複合物及四價錫氯複合物 [MCl₃{CH([superscript i]Pr₂P=S)(C₉H₆N-2)}] [M = Ge (159) 及 Sn (160)] 。而四價硅氯複合物 [SiXCl{CH([superscript i]Pr₂P=S)(C₉H₆N-2)}₂] [X = H (165) 及 Cl (166)] 則由一倍當量的鋰複合物114與一倍當量的SiHCl₃ or SiCl₄生成出來。此外， “開盒型的1,3-雙鍺化環丁烷和“扭曲梯級型的1,3-雙鉛化環丁烷[M{μ²-C([superscript i]Pr₂P=S)(C₉H₆N-2)}]₂ [M = Ge (163) 及 Pb (164)] 是透過複合物114 與半倍當量的GeCl₂1,4-二惡烷或PbCl₂進行复分解反應而生成的。鎂複合物[MgC(PPh₂=S)₂(THF)]₂與一倍當量的SnCl₄ 進行复分解反應並產生了一種新穎的錫化丙二烯 [Sn{C(PPh₂=S)₂}₂] (167) 。化合物153， 156-160， 163-167的結構透過了元素分析、核磁共振波譜和X-射綫單晶衍射表徵。 / 第三章描述由化合物 111 衍生出的過渡金屬及鑭系金屬複合物的合成和結構表徵。透過鋰複合物114與一倍當量的 ZrCl₄或CoCl₂進行复分解反應分別生成了雜配的四價鋯氯複合物 [ZrCl₂{CH(iPr₂P=S)(C₉H₆N-2)}₂] (201)及二價鈷氯複合物 [CoCl{CH(iPr₂P=S)₂(C₉H₆N-2)}]₂ (202) 。透過鉀複合物116與一倍當量的 MCl2 (M = Mn, Fe, Co) 進行复分解反應分別生成了均配的二價錳、二價鈷及二價鐵複合物 [M{CH(iPr₂P=S)C₉H₆N-2}₂] [M = Mn (203) 、Fe (204) 及 Co (205)] 。透過鋰複合物116與一倍當量的CuCl進行复分解反應接著脫氯化氫反應生成了一種史無前例的一價銅簇 [Cu₈{C(iPr₂P=S)(C₉H₆N-2)}₄] (207) 。透過鉀複合物116與一倍當量的LnI₂(THF)₂ (Ln = Eu, Yb) 進行复分解反應分別生成了二聚體均配的二價銪及二價鐿複合物 [Ln{CH(iPr₂P=S)C₉H₆N-2}₂]₂ [Ln = Eu (208) 及Yb (209)] 。化合物201-205，207-209的結構透過了元素分析、核磁共振波譜和X-射綫單晶衍射表徵。 / 第四章描述由化合物 110a及 110b 衍生出的第十四族複合物的合成、結構表徵以及由磷亞胺配位體 2 衍生出的第十四族複合物進行反應活性研究。化合物 110b 與一倍當量的GeCl₂1,4-二惡烷進行脫氯矽烷化的反應生成了二聚體雜配的二價鍺氯複合物 [GeCl{CH₂(Ph₂P=N)(C₉H₆N-2)}]₂ (258) 。化合物 110b 與一倍當量的Pb{N(SiMe₃)₂}₂生成了"扭曲梯級型"的1,3-雙鉛化環丁烷[Pb{μ²-C(iPr₂P=NSiMe₃)(C₉H₆N-2)}]₂ (259)。雙鍺亞乙烯 [(Me₃SiN=PPh₂)₂C=Ge→ Ge=C(PPh₂=NSiMe₃)₂] (214) 與一倍當量的B(C₆F₅)₃.H₂O進行了1,2-加成反應並生成氫氧化二價鍺複合物 [HC(PPh₂=NSiMe₃)₂Ge(OH)B(C₆F₅)₃] (260)。1,3-雙鉛化環丁烷[Pb{μ²-C(Ph₂P=N-SiMe₃)₂}]₂ (215) 與一倍當量的硫磺進行反應並生成硫族二價鉛複合物 [PbS{C(Ph₂P=N-SiMe₃)₂}]₂ (263)。化合物258-260，263的結構透過了元素分析、核磁共振波譜和X-射綫單晶衍射表徵。 / This thesis is focused in two parts: (i) the synthesis and characterization of main- group metal, transition metal and lanthanide metal complexes derived from 2-quinolyl-linked phosphoranosulfide CH₂([superscript i]Pr₂P=S)(C₉H₆N-2) (111) and 2,3-pyrazyl-linked bis(phosphoranosulfide) ligands {CH₂([superscript i]Pr₂P)}₂(C₄H₂N₂-2,3) (113), (ii) the synthesis, characterization and reactivities of group 14 metal complexes derived from different phosphoranoimine ligands, CH₂(PPh₂=NSiMe₃)₂ (2) and CH₂(R₂P=NSiMe₃)(C₉H₆N-2) [R = [superscript i]Pr (110a), R = Ph (110b)]. / Chapter 1 describes the general aspects of phosphoranoimines and phoshoranosulfides as ligands for main group metals, transition metals and lanthanide metals. The synthesis and structural characterization of novel 2-quinolyl-linked (iminophosphorano)methane CH₂(R₂P=NSiMe₃)(C₉H₆N-2) [R = [superscript i]Pr (110a), R = Ph (110b)] and (thiophosphorano)methane CH₂([superscript i]Pr₂P=S)(C₉H₆N-2) (111), and 2,3-pyrazyl-linked (thiophosphorano)methane {CH₂([superscript i]Pr₂P=S)}₂(C₄H₂N₂-2,3) (113) are described. Deprotonation of 111 with [superscript n]BuLi and [superscript n]Bu₂Mg afforded the corresponding 2-quinolyl-linked (thiophosphorano)methanide lithium complex [Li(Et₂O){CH([superscript i]Pr₂P-S)(C₉H₆N-2)}]₂ (114) and magnesium complex [Mg{CH([superscript i]Pr₂P-S) (C₉H₆N-2)}₂] (115), respectively. Compound 114 underwent transmetallation with K[superscript t]BuO to give the potassium salt, [K{CH([superscript i]Pr₂P-S)(C₉H₆N-2)}][subscript n] (116). Deprotonation of 113 with 1 equiv of [superscript n]Bu₂Mg afforded a tetrameric magnesium complex, [Mg{CH([superscript i]Pr₂P=S)}₂C₄H₂N₂-2,3]₄ (118). / Chapter 2 describes the synthesis and structural characterization group 13 and 14 metal complexes derived from compound 111. Deprotonation of 111 with 1 equiv of AlMe₃ afforded the corresponding aluminium complex, [AlMe₂{CH([superscript i]Pr₂P-S) (C₉H₆N-2)}] (153). Furthermore, 2-quinoyl-linked thiophosphinoyl group 14 "open- box" 1,3-dimetallacyclobutane, [M{μ₂-C([superscript i]Pr₂P=S)(C₉H₆N-2)}]₂ [M= Sn (155) and Pb (156)] can be synthesized by deprotonation of 111 with the corresponding group 14 metal(II) amide. 2-Quinolyl-linked thiophosphinoyl group 13 metal complexes [MCl₂{CH([superscript i]Pr₂P-S)(C₉H₆N-2)}] [M = Al (157) and Ga(158)], can be prepared from the metathesis reaction of the lithium complex 114 with 2 equiv of AlCl₃ or GaCl₃. Metathesis reaction of the lithium complex 114 with 2 equiv of GeCl₄ and SnCl₄ afforded the Ge(IV) and Sn(IV) metal complexes, [MCl₃{CH([superscript i]Pr₂P=S)(C₉H₆N-2)}] [M = Ge (159), Sn (160)]. Si(IV) metal complexes [SiXCl{CH([superscript i]Pr₂P=S)(C₉H₆N-2)}₂] [X= H (165), Cl (166)] can also be prepared from 1 equiv of lithium complex 114 with 1 equiv of SiHCl₃ or SiCl₄. Furthermore, 2-quinoyl-linked thiophosphinoyl "open-box" 1,3-germacyclobutane and "twisted-step" 1,3-diplumbacyclobutane, [M{μ₂-C([superscript i]Pr₂P=S)(C₉H₆N-2)}]₂ [M = Ge (163), Pb (164)], are obtained from the metathesis reaction of 114 with GeCl₂1,4-dioxane and PbCl₂, respectively. Metathesis reaction of magnesium methanediide [MgC(PPh₂=S)₂(THF)]₂ (101) with one equiv of SnCl₄ afforded a novel 2-stannaallene [Sn{C(PPh₂=S)₂}₂] (167). The structures of compounds 153, 156-160, 163-167 have been fully characterized by elemental analysis, NMR spectroscopy and X-ray crystallography. / Chapter 3 describes the synthesis and structural characterization of thiophosphinoyl transition metal and lanthanide metal complexes. Metathesis reaction between lithium complex 114 with one equiv of ZrCl₄ and 1 equiv of CoCl₂ afforded heteroleptic chlorozicronium(IV) and chlorocobalt(II) complexes, [ZrCl₂{CH([superscript i]Pr₂P=S) (C₉H₆N-2)}₂] (201) and [CoCl{CH([superscript i]Pr₂P=S)₂(C₉H₆N-2)}]₂ (202), respectively. The reaction of potassium complex 116 with 1 equiv of MCl₂ (M = Mn, Co, Fe) afforded the corresponding homoleptic manganese(II), iron(II) and cobalt(II) complexes [M{CH([superscript i]Pr₂P=S)C₉H₆N-2}₂] [M= Mn(203), Fe(204) and Co(205)], respectively. An unprecedented copper(I) cluster [Cu₈{C([sueprscript i]Pr₂P=S)(C₉H₆N-2)}₄] (207) was prepared from the metathesis reaction of 116 with CuCl followed by dehydrochlorination. Salt metathesis reaction of potassium complex 116 with 1 equiv of LnI₂(THF)₂ (Ln = Yb, Eu) afforded the dimeric homoleptic ytterbium(II) and europium(II) complexes [Ln{CH([superscript i]Pr₂P=S)(C₉H₆N-2)}₂]₂ [Ln= Yb(208), Eu(209)]. Compounds 201-205, 207- 209 have been fully characterized by elemental analysis, NMR spectroscopy and X-ray crystallography. / Chapter 4 describes the synthesis, structural characterization of group 14 metal complexes derived from 2-quinolyl-linked (iminophosphorano)methane and the reactivities of group 14 metal complexes derived from CH₂(PPh₂=NSiMe₃)₂ (2). Compound 110b reacts with 1 equiv of GeCl₂1,4-dioxane underwent dechlorosilylation to give a dimeric heteroleptic chlorogermanium(II) complex [GeCl{CH₂(Ph₂P=N) (C₉H₆N-2)}]₂ (258). Compound 110a reacts with 1 equiv Pb{N(SiMe₃)₂}₂ afforded the "twisted-step" 1,3-diplumbacyclobutane, [Pb{μ²-C([superscript i]Pr₂P=NSiMe₃)(C₉H₆N-2)}]₂ (259). Treatment of bisgermavinylidene [(Me₃SiN=PPh₂)₂C=Ge→Ge=C (PPh₂=NSiMe₃)₂] (214) with B(C₆F₅)₃.H₂O afforded 1,2-addition product, a germanium(II) hydroxide complex [HC(PPh₂=NSiMe₃)₂Ge(OH)B(C₆F₅)₃] (260). Reaction of [Pb{μ²-C(Ph₂P=N-SiMe₃)₂]₂ (215) with elemental sulfur affords lead(II) chalcogenate complex [PbS{C(Ph₂P=N-SiMe₃)₂}]₂ (263). Compounds 258-260, 263 have been fully characterized by elemental analysis, NMR spectroscopy and X-ray crystallography. / 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. / Chan, Yuk Chi. / 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 also in Chinese. / Tables of Contents --- p.ix / Acknowledgments --- p.i / Abstrac --- p.ii / 摘要 --- p.vi / List of Compounds Synthesized --- p.xix / Abbreviations --- p.xxi / Chapter Chapter 1 --- Synthesis and Structural Characterization of Group 1 and 2 Iminophosphinoyl and Thiophosphinoyl Metal Complexes / Chapter 1.1 --- Introduction --- p.1 / Chapter 1.1.1 --- A General Review of Phosphoranoimine Ligands --- p.1 / Chapter 1.1.2 --- Synthesis of Phosphoranoimine --- p.3 / Chapter 1.1.3 --- Neutral Phosphoranoimine Ligands --- p.4 / Chapter 1.1.4 --- Anionic Ligands Derived From Phosphoranoimine --- p.6 / Chapter 1.1.5 --- A General Review of Phosphoranosulfide Ligands --- p.11 / Chapter 1.1.6 --- Synthesis of Phosphoranosulfides --- p.11 / Chapter 1.1.7 --- Neutral Phosphoransulfide Ligands --- p.12 / Chapter 1.1.8 --- Anionic Ligands Derived From Phosphoranosulfide --- p.15 / Chapter 1.1.9 --- A General Review of Group 1 and 2 Metal Complexes Containing Phosphoranosulfide Ligands --- p.19 / Chapter 1.2 --- Objectives of this thesis --- p.23 / Chapter 1.3 --- Results and Discussion --- p.26 / Chapter 1.3.1.1 --- Synthesis of 2-Quinolyl-linked (Iminophosphorano)methane --- p.26 / Chapter 1.3.1.2 --- Spectroscopic Properties of CH₂([superscript i]Pr₂P=NSiMe₃)(C₉H₆N-2) (110a) --- p.27 / Chapter 1.3.1.3 --- Spectroscopic Properties of CH₂(Ph₂P=NSiMe₃)(C₉H₆N-2) (110b) --- p.28 / Chapter 1.3.2.1 --- Synthesis of 2-Quinoly-linked (Thiophosphorano)methane --- p.29 / Chapter 1.3.2.2 --- Spectroscopic properties of CH₂([superscript i]Pr₂P=S)(C₉H₆N-2) (111) --- p.29 / Chapter 1.3.2.3 --- Molecular Structures of CH₂([superscript i]Pr₂P=S)(C₉H₆N-2) (111) --- p.30 / Chapter 1.3.3.1 --- Synthesis of 2,3-Pyrazyl-linked Bis(thiophosphorano)methane --- p.31 / Chapter 1.3.3.2 --- Spectroscopic properties of {CH₂([superscript i]Pr₂P=S)}₂(C₄H₂N₂-2,3) (113) --- p.32 / Chapter 1.3.3.3 --- Molecular Structure of {CH₂([superscript i]Pr₂P=S)}₂(C₄H₂N₂-2,3) (113) --- p.33 / Chapter 1.3.4.1 --- Synthesis of 2-Quinolyl-linked Thiophosphinoyl Lithium Complex --- p.35 / Chapter 1.3.4.2 --- Spectroscopic Properties of [Li(Et₂O){CH([superscript i]Pr₂P-S) (C₉H₆N-2)}]₂ (114) --- p.35 / Chapter 1.3.4.3 --- Molecular Structure of [Li(Et₂O){CH(iPr₂P-S) (C₉H₆N-2)}]₂ (114) --- p.36 / Chapter 1.3.5.1 --- Synthesis of 2-Quinolyl-linked Bis(thiophosphinoyl) Magnesium Complex --- p.38 / Chapter 1.3.5.2 --- Spectroscopic Properties of [Mg{CH([superscript i]Pr₂P-S)(C₉H₆N-2)}₂] (115) --- p.38 / Chapter 1.3.5.3 --- Molecular Structure of [Mg{CH([superscript i]Pr₂P-S)(C₉H₆N-2)}₂] (115) --- p.39 / Chapter 1.3.6.1 --- Synthesis of 2-Quinolyl-linked Thiophosphinoyl Potassium Complex --- p.41 / Chapter 1.3.6.2 --- Spectroscopic Properties of [K{CH([superscript i]Pr₂P-S)(C₉H₆N-2)}][subscript n] (116) --- p.41 / Chapter 1.3.6.3 --- Molecular Structure of [K{CH([superscript i]Pr₂P-S)(C₉H₆N-2)}][subscript n] (116) --- p.42 / Chapter 1.3.7.1 --- Synthesis of 2,3-pyrazyl-linked Bis(thiophosphinoyl) Magnesium Complex --- p.44 / Chapter 1.3.7.2 --- Spectroscopic Properties of [Mg{CH([superscript i]Pr₂P-S)}₂(C₄H₂N₂-2,3)]₄ (118) --- p.45 / Chapter 1.3.7.3 --- Molecular Structures of [Mg{CH([superscript i]Pr₂P-S)}₂(C₄H₂N₂-2,3)]₄ (118) --- p.45 / Chapter 1.4 --- Experimental Section for Chapter 1 --- p.49 / Chapter 1.5 --- References for Chapter 1 --- p.56 / Chapter Chapter 2 --- Synthesis and Structural Characterization of Thiophosphinoyl Group 13 and 14 Metal Complexes / Chapter 2.1 --- Introduction --- p.66 / Chapter 2.1.1 --- A General Review of Group 13 Metal Complexes Containing Phosphoranosulfide Ligands --- p.65 / Chapter 2.1.2 --- A General Review of Group 14 Metal Complexes Containing Phosphoranosulfide Ligands --- p.71 / Chapter 2.2 --- Results and Discussion --- p.75 / Chapter 2.2.1.1 --- Synthesis of 2-Quinolyl-linked Thiophosphinoyl Aluminium Complex --- p.75 / Chapter 2.2.1.2 --- Spectroscopic Properties of [AlMe₂{CH([superscript i]Pr₂P-S) (C₉H₆N-2)}] (153) --- p.75 / Chapter 2.2.1.3 --- Molecular Structures of [AlMe₂{CH([superscript i]Pr₂P-S)(C₉H₆N-2)}₂] (153) --- p.76 / Chapter 2.2.2.1 --- Synthesis of "Open-box" 2-Quinolyl-linked Thiophosphinoyl 1,3-distannacyclobutane and 1,3-diplumbacyclobutane --- p.78 / Chapter 2.2.2.2 --- Spectroscopic Properties of "Open-box" [Sn{{471}²-C([superscript i]Pr₂P=S)(C₉H₆N-2)}]₂ (155) and [Pb{μ²-C([superscript i]Pr₂P=S) (C₉H₆N-2)}]₂ (156) --- p.79 / Chapter 2.2.2.3 --- Molecular Structure of "Open-box" [Sn{{471}²-C([superscript i]Pr₂P=S)(C₉H₆N-2)}]₂ (155) and [Pb{μ²-C([superscript i]Pr₂P=S) (C₉H₆N-2)}]₂ (156) --- p.81 / Chapter 2.2.3.1 --- Synthesis of 2-Quinolyl-linked Thiophosphinoyl Group 13 Metal Complexes --- p.86 / Chapter 2.2.3.2 --- Spectroscopic Properties of [AlCl₂{CH([superscript i]Pr₂P-S)(C₉H₆N-2)}] (157) --- p.86 / Chapter 2.2.3.3 --- Molecular Structures of [AlCl₂{CH([superscript i]Pr₂P-S)(C₉H₆N-2)}] (157) --- p.87 / Chapter 2.2.3.4 --- Spectroscopic Properties of [GaCl₂{CH([superscript i]Pr₂P-S)(C₉H₆N-2)}] (158) --- p.89 / Chapter 2.2.3.5 --- Molecular Structures of [GaCl2{CH([superscript i]Pr₂P-S)(C₉H₆N-2)}] (158) --- p.89 / Chapter 2.2.4.1 --- Synthesis of 2-Quinolyl-linked Thiophosphinoyl Group 14 Metal Complexes --- p.91 / Chapter 2.2.4.2 --- Spectroscopic Properties of [GeCl₃{CH([superscript i]Pr₂P=S)(C₉H₆N-2)}] (159) --- p.94 / Chapter 2.2.4.3 --- Molecular Structure of [GeCl₃{CH([superscript i]Pr₂P=S)(C₉H₆N-2)}] (159) --- p.95 / Chapter 2.2.4.4 --- Spectroscopic Properties of [SnCl₃{CH([superscript i]Pr₂P=S)(C₉H₆N-2)}] (160) --- p.96 / Chapter 2.2.4.5 --- Molecular Structure of [SnCl₃{CH([superscript i]Pr₂P=S)(C₉H₆N-2)}] (160) --- p.97 / Chapter 2.2.4.6 --- Spectroscopic Properties of [Ge{{471}²-C([superscript i]Pr₂P=S)(C₉H₆N-2)}]₂ (163) --- p.99 / Chapter 2.2.4.7 --- Molecular Structure of [Ge{{471}²-C([superscript i]Pr₂P=S)(C₉H₆N-2)}]₂ (163) --- p.100 / Chapter 2.2.4.8 --- Spectroscopic Properties of "Twisted-step" [Pb{{471}²-C([superscript i]Pr₂P=S)(C₉H₆N-2)}]₂ (164) --- p.102 / Chapter 2.2.4.9 --- Molecular Structure of "Twisted-step" [Pb{{471}²-C([superscript i]Pr₂P=S)(C₉H₆N-2)}]₂ (164) --- p.103 / Chapter 2.2.4.10 --- Spectroscopic Properties of [SiHCl{CH([superscript i]Pr₂P=S) (C₉H₆N-2)}₂] (165) --- p.105 / Chapter 2.2.4.11 --- Molecular Structure of [SiHCl{CH([superscript i]Pr₂P=S)(C₉H₆N-2)}₂] (165) --- p.106 / Chapter 2.2.4.12 --- Spectroscopic Properties of [SiCl₂{CH([superscript i]Pr₂P=S)(C₉H₆N-2)}2] (166) --- p.107 / Chapter 2.2.4.13 --- Molecular Structure of [SiCl₂{CH([superscript i]Pr₂P=S)(C₉H₆N-2)}₂] (166) --- p.108 / Chapter 2.2.5.1 --- Synthesis of a Tin Analogue of Allene from Bis(diphenylthiophosphinoyl)magnesium methanediide --- p.110 / Chapter 2.2.5.2 --- Spectroscopic Properties of [Sn{C(PPh₂=S)₂}₂] (167) --- p.110 / Chapter 2.2.5.3 --- Molecular Structure of [Sn{C(PPh₂=S)₂}₂] (167) --- p.113 / Chapter 2.2.6.1 --- Synthesis of 1,3-diplumbacyclobutane from Bis(diphenylthiophosphinoyl)magnesium methanediide --- p.115 / Chapter 2.3 --- Experimental Section for Chapter 2 --- p.117 / Chapter 2.4 --- References for Chapter 2 --- p.128 / Chapter Chapter 3 --- Synthesis and Structural Characterization of Thiophosphinoyl Transition Metal and Lanthanide Metal Complexes / Chapter 3.1 --- Introduction --- p.133 / Chapter 3.1.1 --- A General Review of Transition Metal Complexes Containing Phosphoranosulfide Ligands --- p.133 / Chapter 3.1.2 --- A General Review of Organolanthanide Complexes --- p.139 / Chapter 3.1.3 --- A General Review of Lanthanide Metal Complexes Containing Phosphoranosulfide Ligands --- p.144 / Chapter 3.2 --- Results and Discussion --- p.147 / Chapter 3.2.1.1 --- Synthesis of 2-Quinolyl-linked Chloro(thiophosphorano) methanide Zirconium(IV) Complex --- p.147 / Chapter 3.2.1.2 --- Spectroscopic Properties of [ZrCl₂{CH([superscript i]Pr₂P=S)(C₉H₆N-2)}₂] (201) --- p.147 / Chapter 3.2.1.3 --- Molecular Structures of [ZrCl₂{CH([superscript i]Pr₂P=S)(C₉H₆N-2)}₂] (201) --- p.148 / Chapter 3.2.2.1 --- Synthesis of 2-Quinolyl-linked Chloro(thiophosphorano) methanide Cobalt(II) Complex --- p.151 / Chapter 3.2.2.2 --- Spectroscopic Properties of [CoCl{CH([superscript i]Pr₂P=S)(C₉H₆N-2)}]₂ (202) --- p.151 / Chapter 3.2.2.3 --- Molecular Structures of [CoCl{CH([superscript i]Pr₂P=S)(C₉H₆N-2)}]₂ (201) --- p.152 / Chapter 3.2.3.1 --- Synthesis of 2-Quinolyl-linked (Thiophosphorano)methanide Late Transition Metal Complexes --- p.154 / Chapter 3.2.3.2 --- Spectroscopic Properties of [Mn{CH(iPr₂P-S)(C₉H₆N-2)}₂] (203) [Fe{CH([superscript i]Pr₂P-S)(C₉H₆N-2)}2] (204) and [Co{CH([superscript i]Pr₂P-S)(C₉H₆N-2)}2] (205) --- p.155 / Chapter 3.2.3.3 --- Molecular Structure of [Mn{CH([superscript i]Pr₂P-S)(C₉H₆N-2)}₂] (203) --- p.155 / Chapter 3.2.3.4 --- Molecular Structure of [Fe{CH([superscript i]Pr₂P-S)(C₉H₆N-2)}₂] (204) and [Co{CH([superscript i]Pr₂P-S)(C₉H₆N-2)}2] (205) --- p.158 / Chapter 3.2.4.1 --- Synthesis of a Novel 2-Quinolyl-linked (Thiophosphorano) methanediide Copper(I) Cluster --- p.161 / Chapter 3.2.4.2 --- Spectroscopic Properties of [Cu₈{C([superscript i]Pr₂P-S)(C₉H₆N-2)}₄] (207) --- p.163 / Chapter 3.2.4.3 --- Molecular Structure of [Cu₈{C([superscript i]Pr₂P-S)(C₉H₆N-2)}₄] (207) . --- p.164 / Chapter 3.2.5.1 --- Synthesis of 2-Quinolyl-linked Bis(thiophosphorano)methanide Lanthanide(II) Complexes --- p.171 / Chapter 3.2.5.2 --- Spectroscopic Properties of [Yb{CH([superscript i]Pr₂P-S)(C₉H₆N-2)}₂]₂ (208) --- p.172 / Chapter 3.2.5.3 --- Molecular Structure of [Yb{CH([superscript i]Pr₂P-S)(C₉H₆N-2)}₂]₂ (208) . --- p.172 / Chapter 3.2.5.4 --- Spectroscopic Properties of [Eu{CH([superscript i]Pr₂P-S)(C₉H₆N-2)}₂]₂ (209) --- p.175 / Chapter 3.2.5.5 --- Molecular Structure of [Eu{CH([superscript i]Pr₂P-S)(C₉H₆N-2)}₂]₂ (209).... --- p.175 / Chapter 3.3 --- Experimental Section for Chapter 3 --- p.178 / Chapter 3.4 --- References for Chapter 3 --- p.184 / Chapter Chapter 4 --- Synthesis, Structure and Reactivity of Iminophosphinoyl Group 14 Metal Complexes / Chapter 4.1 --- Introduction --- p.192 / Chapter 4.1.1 --- A General Review of Low-Valent Group 14 Metal Complexes bearing phosphoranoimine as the supporting ligands --- p.192 / Chapter 4.1.2 --- A General Review of Bisgermavinylidene and 1,3-dimetallacyclobutane --- p.196 / Chapter 4.2 --- Results and discussion --- p.206 / Chapter 4.2.1.1 --- Synthesis of 2-Quinolyl-linked Chloro(iminophosphorano) methane Germanium(II) Complex --- p.206 / Chapter 4.2.1.2 --- Spectroscopic Properties of [GeCl{CH₂(Ph₂P=N)(C₉H₆N-2)}]₂ (258) --- p.207 / Chapter 4.2.1.3 --- Molecular Structure of [GeCl{CH₂(Ph₂P=N)(C₉H₆N-2)}]₂ (258) --- p.208 / Chapter 4.2.2.1 --- Synthesis of "Twisted-step" 2-Quinolyl-linked (Iminophosphinoyl) 1,3-diplumbacyclobutane --- p.210 / Chapter 4.2.2.2 --- Spectroscopic Properties of [Pb{{471}²-C(iPr₂P=NSiMe₃)(C₉H₆N-2)}]₂ (259) --- p.210 / Chapter 4.2.2.3 --- Molecular Structure of [Pb{{471}²-C([superscript i]Pr₂P=NSiMe₃)(C₉H₆N-2)}]₂ (259) --- p.211 / Chapter 4.2.3.1 --- Synthesis of Lewis acid stabilized Germanium(II) hydroxide from Bisgermavinylidene --- p.213 / Chapter 4.2.3.2 --- Spectroscopic Properties of [HC(PPh₂=NSiMe₃)₂Ge(OH) B(C₆F₅)₃] (260) --- p.214 / Chapter 4.2.3.3 --- Molecular Structure of [HC(PPh₂=NSiMe₃)₂Ge(OH)B(C₆F₅)₃] (260) --- p.215 / Chapter 4.2.4.1 --- Synthesis of Lead(II) Chalcogenate complex from 1,3-diplumbacyclobutane --- p.217 / Chapter 4.2.4.2 --- Spectroscopic Properties of [PbS{C(PPh₂=NSiMe₃)₂}]₂ (263) --- p.218 / Chapter 4.2.4.3 --- Molecular structure of [PbS{C(PPh₂=NSiMe₃)₂}]₂ (263) --- p.219 / Chapter 4.3 --- Experimental Section for Chapter 4 --- p.222 / Chapter 4.4 --- References for Chapter 4 --- p.226 / Appendix I / Chapter A. --- General Procedures --- p.231 / Chapter B. --- Physical and Analytical Measurements --- p.231 / Chapter Appendix II / Chapter Table A.1. --- Selected Crystallographic Data for Compounds 111, 113-115 --- p.234 / Chapter Table A.2. --- Selected Crystallographic Data for Compounds 116, 118, 153 and 155 --- p.235 / Chapter Table A.3. --- Selected Crystallographic Data for Compounds 156-159 --- p.236 / Chapter Table A.4. --- Selected Crystallographic Data for Compounds 160, 163-165 --- p.237 / Chapter Table A.5. --- Selected Crystallographic Data for Compounds 166, 167, 201 and 202 --- p.238 / Chapter Table A.6. --- Selected Crystallographic Data for Compounds 203-205 and 207 --- p.239 / Chapter Table A.7. --- Selected Crystallographic Data for Compounds 208, 209, 258 and 259 --- p.240 / Chapter Table A.8. --- Selected Crystallographic Data for Compounds 260 and 263 --- p.241

The aim of the work described in this thesis was to develop a more extensive knowledge of the chemistry of neptunium compounds by making rare, air- and moisture sensitive, low formal oxidation state neptunium compounds with full structural and synthetic characterization. The thesis contains three results chapters. Chapter one introduces neptunium chemistry as a background to the results presented. The first review on the molecular non-aqueous neptunium chemistry is provided and the literature reports to date discussed in the context of this. Chapter two describes exploratory synthetic and structural investigations of the organoneptunium complexes supported by the cyclopentadienyl anion, Cp = (C5H5)-, and the (trimethylsilyl)cyclopentadienyl anion, Cp' = (C5H4[Si(CH3)3])-. The syntheses of [Np(Cp)3]n and Np(Cp')3 complexes are detailed and the effect of the trimethylsilyl group of the ligand on the structure and reactivity have been investigated. Complexes were characterized by single crystal X-ray diffractometry, NMR and ATR(IR) spectroscopy. Both organoneptunium complexes were studied in reactions designed to expand the neptunium redox envelope. Notably, the complex Np(Cp')3 is reduced by KC8 in the presence of 2.2.2-cryptand to afford a product assigned as neptunium(II) complex, K(2.2.2-cryptand)[Np(Cp')3] that is thermally very unstable above approx. -10 ºC, in direct analogy to previously reported uranium, thorium and lanthanide complexes of the general formula, K(2.2.2-cryptand)[M(Cp')3]. The reaction between Np(Cp)3Cl and KCp in THF afforded the unanticipated K[NpIII(Cp)4] product as a result of a single-electron reduction presumably arising from Np–C σ-bond homolysis reactivity. This behaviour appears to be unique amongst the actinides for the An(IV)/An(III) redox couple. Chapter three focuses on oxo-bridged homo and heterometallic complexes. The reaction of NpCp3 with dioxygen afforded not only the simple oxide, (μ-O)[An(Cp)3]2, but also a small quantity of the unexpected new trinuclear oxo- neptunium(IV) compound [{(Cp3Np)(μ-O)}2{Np(Cp)2}], which interestingly contains the rare C2v-symetric [An(Cp)2]2+ structural moiety. This oxo-bridged environment is not paralleled in uranium chemistry. The two isostructural oxides, (μ-O)[An(Cp)3]2 (An = U, Np), allow a comparative study of the magnetic exchange phenomena between the two actinide centres demonstrating an exceedingly strong antiferromagnetic coupling, which is largely independent of the communicated Kramers NpIV (5f3, 4I9/2) or non-Kramers UIV (5f2, 3H4) ions. To design heterobimetallic systems, the uranyl(VI) complexes, [(UVIO2)(THF)(H2L)], supported by the calix[4]pyrrole Schiff base macrocycles, H4LOct and H4LEt, were singly-reduced to uranyl(V) with either of the actinide complexes Np(Cp)3 or U(Cp)3, affording isostructural [(Cp3)AnIVOUVO(THF)(H2L)]. Preliminary investigations of the magnetism of the AnIV-O-UV are reported, although their analysis gave counterintuitive results. Chapter four explores the redox chemistry and molecular and electronic structure of neptunium(III) complexes of the doubly deprotonated trans-calix[2]benzene[2]pyrrole, H2(LAr), macrocycle which has a unique π-bonding potential and conformational flexibility. Interestingly, the reactions with neptunium(IV) chloride yielded mono- and dinuclear neptunium(III) complexes, [(LAr)NpCl] and [(LAr)Np2Cl4(THF)3], with a subsequent elimination of the ligand radical; both complexes adopted η6:κ1:η6:κ1 bis(arene) sandwiched structural motif. In a direct analogy to the redox behaviour occurring in the salt metathesis between Np(Cp)3Cl and KCp, the spontaneous reduction derives from the favourable Np(IV)/Np(III) redox system. The reduction of complex [(LAr)NpCl] with NaK3 in DME produces near-black solutions consistent with [NpII(LAr)(DME)] that in the absence of excess NaK3 gradually convert to the metallated (LAr-H)3- neptunium(III) complex, [K(DME)(LAr-H)NpIII(OMe)]2, featuring the actinide centre bound with a ‘metallocene-type’ geometry provided by the two η5-bound pyrrolides of the ligand. The neptunium(III) compounds were characterized in the solid state by single crystal X-ray diffractometry, ATR(IR) spectroscopy and in a solution by NMR and UV-Vis-NIR spectroscopy.

Les métallodendrimères sont des macromolécules précises contenant des centres métalliques dont les propriétés sont exploitables pour la fabrication de nanodevices utiles en catalyse, reconnaissance moléculaire et en tant que précurseurs de nanoparticules. Pour leur contruction, de nouvelles réactions ont été mises au point à partir d’alcynes organométalliques électrophiles qui ont permis la formation de liaisons C-C, C-N et M=C, mettant en jeu des métallocènes du fer, du ruthénium et du cobalt. Cette ingéniérie moléculaire a conduit à de nouvelles métallo-étoiles, dendrimères et nanoparticules d’or aux propriéties rédox originales. / Metallodendrimers are precise macromolecules containing metallic centers with properties that are exploitable for nanodevice fabrication providing uses in catalysis, molecular recognition and as nanoparticle precursors. For their construction, new reactions have been disclosed from electrophilic organometallic alkynes leading to the formation of C-C, C-N and C=C bonds that involve iron, ruthenium and cobalt metallocenes. This molecular engineering has produced new metallo-stars, metallodendrimers and gold nanoparticles with original redox properties.

by Kin Wah Mak. / Thesis (Ph.D.)--Chinese University of Hong Kong, 1998. / Includes bibliographical references (p. 180-195). / 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.