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
| Identifer | oai:union.ndltd.org:cuhk.edu.hk/oai:cuhk-dr:cuhk_328130 |
| Date | January 2013 |
| Contributors | Chan, Yuk Chi., Chinese University of Hong Kong Graduate School. Division of Chemistry. |
| Source Sets | The Chinese University of Hong Kong |
| Language | English, Chinese |
| Detected Language | English |
| Type | Text, bibliography |
| Format | electronic resource, electronic resource, remote, 1 online resource (xxii, 241 leaves) : ill. (some col.) |
| Rights | Use of this resource is governed by the terms and conditions of the Creative Commons “Attribution-NonCommercial-NoDerivatives 4.0 International” License (http://creativecommons.org/licenses/by-nc-nd/4.0/) |
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