The hydrolysis of 4-Nitrophenylphosphate (NPP) as model substrate in the presence of several cobalt (III) amine [N4Co(OH)(H2O)]2+ and copper bipyridyl [Cu(bpy)(H2O)2]2+ complexes in oil in water microemulsion media was investigated. The reaction was monitored by measuring the absorbance of the nitrophenolate ion produced in the reaction aliquots with time under the experimental conditions. The order of effectiveness of the microemulsion systems towards the hydrolysis of NPP in the presence of these metal ions were found to be cationic > anionic > aqueous at neutral pH. The results of the present investigation exhibits stoichiometric turnovers for the 1:1, 2:1 and 3:1 cobalt to NPP ratio and catalytic turnovers for the [Cu(bpy)2+ to NPP ratio of 1:20. Catalysis in the microemulsion mediated reaction solutions was evident even in low concentrations of the metal ions in 1:2000 metal to NPP ratio. An explanation for the enhanced catalytic activity of the [Cu(bpy)(OH)(H2O)]2+ complex for the hydrolysis of NPP is afforded and the application of the above model systems for possible environmental decontamination of toxic organophosphates is anticipated. / Chemistry / M.Sc. (Chemistry)

Chapter one reviews the recent progress in the synthesis of phosphonopeptides, pseudopeptides containing a phosphinic, phosphonic or phosphonamide linkage in place of an amide (peptide) linkage. It describes some of the general methods for the synthesis of these pseudopeptides; for example through couplings to the nitrogen of an ¿-aminophosphonic acid, or Michael addition to acrylates, as well as other methods, the scope for which are not as wide yet. It also provides a summary of the reported biological activities of this class of pseudopeptides. Chapter two contains the results and discussion for a novel method for the synthesis of ¿-hydroxy phenylphosphinate oligomers as well as hybrid oligomers containing ¿-hydroxy phenylphosphinic acid and ¿-amino carboxylic acids. In particular, synthesis of a series of dimeric ¿-hydroxy phenylphosphinates are reported. The analysis of these dimers by a combination of NMR spectroscopy, X-ray crystallography and computational methods shows intramolecular hydrogen bonding in these molecules depends on the relative configuration of the carbon and phosphorus atoms. However, although the development of the synthetic methods was successful, the separation and isolation of the diastereomers was not always possible, which hindered a more comprehensive analysis of folding patterns in these molecules. Chapter three contains the experimental procedures, preparation and spectroscopic characterisation of all the chemical compounds. Crystal data and details of crystal structures are in the Appendix. / EPSRC

No description available.

Certain organophosphorus compounds have the ability to induce a delayed neuropathic condition in sensitive species termed organophosphorus compound-induced delayed neurotoxicity (OPIDN). Esteratic changes associated with OPIDN have been successfully modeled in vitro. The physical characteristics of lesion development in OPIDN including the mode of nerve cell death, cytotoxic initiator and effector molecules, and cytoskeletal involvement have received little in vitro investigation. This dissertation evaluated the mode of cell death (apoptosis versus oncotic-necrosis), and cell cycle, cytoskeletal, nuclear, and mitochondrial alterations induced by OP compounds in SH-SY5Y cultures, an in vitro human neuroblastoma model. The distribution of in vivo neural degeneration in white Leghorn hen models was also assessed as a prelude to validating the mode of OP compound-induced in vivo neural cell death. These endpoints were evaluated by utilizing flow cytometry, spectrophotometry, gel electrophoresis, immunohistochemistry, light, and electron microscopy. Initial data gathered on culture parameters revealed that the mitotic status, basal rates of cell death, and total culture density were dependent on the condition of the media and the initial seeding density. Subsequent in vitro investigations used standardized culture conditions with OP compounds (diisopropylphosphorofluoridate (DFP), paraoxon, parathion, phenyl saligenin phosphate (PSP), tri-ortho-tolyl phosphate (TOTP), and triphenyl phosphite (TPPi); 1uM - 1mM). These studies revealed that OP compounds altered the cell cycle phase, decreased the amount of intracellular f-actin, altered the mitochondrial membrane potential, and induced caspase-3 activation and nuclear partitioning characteristic of apoptosis. The amount of change in these parameters was strongly dependent on the OP compound, the length of incubation time, and the presence of modulators of cytotoxicity such as phenylmethylsulfonyl fluoride (PMSF), carbachol, Ac-DEVD-CHO, Ac-IETD-CHO, and cyclosporin A. Preliminary in vivo experiments designed to validate in vitro results revealed neural degeneration involving fibers, terminals, and cell soma in spinal cord and brain tissue of PSP- and TPPi- exposed hens. The distribution and magnitude of these changes were contingent on the OP compound and length of time post-exposure. Subsequent experiments designed to evaluate the mode of cell death in these tissues revealed little evidence of either necrosis or apoptosis. These results, therefore, did not support or refute in vitro observations. Many OP compound-induced subcellular alterations have been demonstrated in our in vitro SH-SY5Y neuroblastoma model. Even though the mode of cell death observed in SH-SY5Y cells was not validated in in vivo experiments, in vitro observations nonetheless provide stimulating areas to further research the mechanisms of OPIDN and OP compound-induced cell death. / Ph. D.

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The study of rapid cleavage of organophosphate esters by metal ions is of great interest as it is the most important reaction in both biological and environmental sciences. A good understanding of organophosphate hydrolysis by metal ions is important as it can be exploited in formulation of useful detoxifying agents for organophosphate contaminants in the environment. The knowledge can also help in developing effective artificial enzymes. The hydrolysis of 4-NPP in the presence of Ferrous and Ferric ions in o/w microemulsion media was investigated. The reaction was monitored by measuring the absorbance of the 4-nitrophenolate ion produced in the reaction aliquots with time. The order of effectiveness of the ME media towards the hydrolysis of 4-NPP was found to be CME > AME > aqueous in the presence of Fe(II), Fe(III) and Prussian blue at neutral pH. In comparison with individual metal ions used in the investigation, it was found that polymetallic Prussian blue showed enhanced rate of hydrolysis. The degree of effectiveness is as follows; Prussian blue (insoluble) > Prussian blue (soluble) > Fe(III) > Fe(II). The result of the present investigation enriches our understanding of the possible roles polymetallic ions play in hydrolysis reactions and the effect of different reaction media. The reactions mimic the roles of purple acid phosphatases in the hydrolysis of phosphate esters. The application of the above systems for environmental decontamination of organophosphates is also envisaged. / Chemistry / M.Sc.(Chemistry)

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

Ho, Ming Gong. / "October 2009." / Thesis (M.Phil.)--Chinese University of Hong Kong, 2010. / Includes bibliographical references (leaves 72-75). / Abstracts in English and Chinese. / Table of Contents --- p.V / Acknowledgements --- p.i / Abstract --- p.ii / 摘要 --- p.iv / List of Compounds Synthesized --- p.X / Abbreviation --- p.xi / Chapter Chapter 1 --- Synthesis and Characterization of (9-Anthryl)(iminophosphorano)methanide Group 14 Metal Complexes / Chapter 1.1 --- Introduction --- p.1 / Chapter 1.1.1 --- A General Review of Phosphoranoimine Ligands --- p.1 / Chapter 1.1.2 --- A General Review of Group 14 Metal Complexes Containing Phosphoranoimine Ligands --- p.8 / Chapter 1.2 --- Objectives --- p.9 / Chapter 1.3 --- Results and Discussion --- p.10 / Chapter 1.3.1.1 --- Synthesis of (9-Anthryl)(iminophosphorano)methanide Germanium(II) Chloride [Ge{CH(Pri2P=NSiMe3)(Anth)}Cl] (44) and (9-Anthryl)(iminophosphorano)methanide Tin(II) Chloride [Sn{CH(Pri2P=NSiMe3)(Anth)}Cl] (45) --- p.10 / Chapter 1.3.1.2 --- Spectroscopic Properties of 44 and 45 --- p.11 / Chapter 1.3.1.3 --- Molecular Structures of [Ge {CH(Pri2P=NSiMe3)(Anth)} Cl] (44) and [Sn{CH(Pri2P=NSiMe3)(Anth)} Cl] (45) --- p.11 / Chapter 1.3.2.1 --- Synthesis of Homoleptic Dialkylstannylene [Sn{CH(Pr/2P=NSiMe3)(Anth)}2] (46) --- p.16 / Chapter 1.3.2.2 --- Spectroscopic Properties of 46 --- p.17 / Chapter 1.3.2.3 --- Molecular Structure of [Sn{CH(Pri2P=NSiMe3)(Anth)}2] (46) --- p.17 / Chapter 1.4 --- Experimental Section --- p.20 / Chapter 1.5 --- References for Chapter 1 --- p.23 / Chapter Chapter 2 --- "Synthesis, Characterization and Catalytic Study of (9-Anthryl)(iminophosphorano)methanide Group 4 Metal Complexes" / Chapter 2.1 --- Introduction --- p.27 / Chapter 2.1.1 --- A General Review of Group 4 Metallocene Catalysts in Olefin Polymerization --- p.27 / Chapter 2.1.2 --- A General Review of Group 4 Metal Complexes --- p.28 / Chapter 2.2 --- Results and Discussion --- p.31 / Chapter 2.2.1.1 --- Synthesis of (9-Anthryl)(iminophosphorano)methanide Zirconium(IV) Chloride [Zr{CH(Pri2P=NSiMe3)(Anth)} 2CI2] (57) and (9-Anthryl)(iminophosphorano)methanide Hafnium(IV) Chloride [Hf{CH(Pri2P=NSiMe3)(Anth)}2Cl2] (58) --- p.31 / Chapter 2.2.1.2 --- Spectroscopic Properties of 57 and 58 --- p.32 / Chapter 2.2.1.3 --- Molecular Structures of [Zr{CH(Pri2P^NsiMe3)(Anth)}2CI2] (57) and [Hf{CH(Pri2P=NsiMe3)(Anth)}2Cl2] (58) --- p.32 / Chapter 2.3 --- Catalytic Study of Compounds 57 and 58 on Ethylene Polymerization --- p.37 / Chapter 2.4 --- Experimental Section --- p.39 / Chapter 2.5 --- Reference for Chapter 2 --- p.41 / Chapter Chapter 3 --- "Synthesis, Characterization and Catalytic Study of (9-Anthryl)(thiophosphinoyl)methanide Metal Complexes" / Chapter 3.1 --- Introduction --- p.45 / Chapter 3.2 --- A General Review of Phosphoranosulfide Ligands --- p.45 / Chapter 3.3 --- Objectives --- p.54 / Chapter 3.4 --- Results and Discussion --- p.55 / Chapter 3.4.1.1 --- Synthesis of (9-Anthryl)(thiophosphinoyl)methane [CH2(Pri2P=S)(Anth)] (92) and Lithium Compound [Li(THF)2{CH(Pr/2P=S)(Anth)}] (93) --- p.55 / Chapter 3.4.1.2 --- Spectroscopic Properties of 92 and 93 --- p.56 / Chapter 3.4.1.3 --- Molecular Structures of [Li(THF)2{CH(Pri2P=S)(Anth)}] (93) --- p.57 / Chapter 3.4.2.1 --- Synthesis of Germylgermylene [Ge(GeCl){CH(Pri2P=S)(Anth)}2C12C6H5CH3] (94) --- p.59 / Chapter 3.4.2.2 --- Spectroscopic Properties of 94 --- p.61 / Chapter 3.4.2.3 --- Molecular Structure of [Ge(GeCl){CH(Pri2P=S)(Anth)}2Cl2C6H5CH3] (94) --- p.61 / Chapter 3.4.3.1 --- Synthesis of (9-Anthryl)(thiophosphinoyl)methanide Zirconium(IV) Complex [Zr{CH(Pri2P=S)(Anth)}2Cl2(THF) THF] (95) --- p.64 / Chapter 3.4.3.2 --- Spectroscopic Properties of 95 --- p.64 / Chapter 3.4.3.3 --- Molecular Structure of [Zr{CH(Pri2P=S)(Anth)}2Cl2(THF) THF] (95) --- p.65 / Chapter 3.4.3.4 --- Catalytic Study of [Zr{CH(Pri2P=S)(Anth)}2Cl2(THF) THF] (95)i --- p.68 / Chapter 3.5 --- Experimental Section --- p.69 / Chapter 3.6 --- References for Chapter 3 --- p.72

Reported here is an investigation to determine if azinphos-methyl (AZM), an organophosphate insecticide, adducts to hemoglobin, and if so, whether the hemoglobin adduct could be used as a quantitative marker of occupational AZM exposure. We hypothesized that AZM, or a metabolite of AZM, binds to hemoglobin in erythrocytes forming an adducted protein. We administered radiolabled AZM to rats and found a stable, dose-dependent association of radioactivity with hemoglobin. The decline in hemoglobin-associated radioactivity followed the expected kinetics of erythrocyte turnover in rats. We examined hemoglobin isolated from these rats by high-pressure liquid chromatography, liquid scintillation counting, and electrospray ionization mass spectrometry. These analyses provided evidence of AZM or an AZM metabolite binding to one of the beta proteins of hemoglobin. In vitro incubation of AZM with hemoglobin in a liver microsome system indicated an AZM adduct to heme. Further research is necessary to fully characterize the adduct and determine whether this biomarker will be useful for monitoring human exposure to AZM. / Graduation date: 2000