本項研究工作主要對五個結構類似的胍基配體， 即 [(2,6-Me₂C₆H₃N)C(NHPri)(NPri)]⁻ (L¹)， [(2,6-Me₂C₆H₃N)C(NHCy)(NCy)]⁻ (L²)， [(2,6-Me₂C₆H₃N)C{N(SiMe₃)Cy}(NCy)]⁻ (L³)， [(2,6-Pri₂C₆H₃N)C{N(SiMe₃)₂}(NC₆H₃Pri₂-2,6)]⁻ (L⁴) 和 [(2,6-Pri₂C₆H₃N)C(NEt₂)(NC₆H₃Pri₂-2,6)]⁻ (L⁵) 與二價鉻以及二價鑭系金屬[Sm(II)、Eu(II) 及 Yb(II)] 的配位化學進行研究，同時，一系列由 L¹ 配體所衍生的三價鑭系金屬配合物亦成功被合成。 / 第一章概括介紹了由胍基配體所構築的金屬配合物的研究背景。 / 第二章敍述了含 L¹ 與 L⁴ 的二價鉻配合物的合成、結構及其化學反應。 通過胍基鉀化合物 [KL¹･0.5PhMe] (1) 與二氯化鉻反應可得到單核二價鉻雙胍基配合物 [Cr(L¹)₂] (3)。 通過胍基鋰化合物 [LiL⁴(Et₂O)] (2) 與二氯化鉻反應，成功製備了單胍基二價鉻配合物 [Cr(L⁴)(μ-Cl)₂Li(THF)(Et₂O)] (4)。 而把二價鉻配合物 4於甲苯溶液中重結晶可得到二聚體的二價鉻配合物 [{Cr(L⁴)(μ-Cl)}₂] (5)。 另外，我們對二價鉻配合物 3 及 4 的反應特性也進行了研究。 [Cr(L¹)₂] (3) 與單質碘、二苯基硫族化合物 PhEEPh (E = S, Se, Te) 以及叠氮金剛烷反應可得相對應的三價鉻混合配體化合物，分別爲 [Cr(L¹)₂I] (6)、[Cr(L¹)₂(EPh)] [E = S (7), Se (8), Te (9)]，及四價鉻配合物 [Cr(L¹)₂{N(1-Ad)}] (10)。 透過單胍基二價鉻配合物 [Cr(L⁴)(μ-Cl)₂Li(THF)(Et₂O)] (4) 與 NaOMe反應可得甲氧基-胍基配合物 [{Cr(L⁴)(μ-OMe)}₂] (11)。 / 第三章主要報導含 L¹， L²， L³ 和 L⁵ 配基的二價鑭系配合物的合成、結構和化學反應特性。 透過 [LnI₂(THF)₂] (Ln = Sm, Eu, Yb) 與胍基鉀鹽反應，我們成功合成一系列二價鑭系絡合物，包括 [{Eu(L¹)(μ-L¹)}₂] (15)， [{Ln(L²)(μ-L²)}₂･nC₆H₁₄] [Ln = Eu, n = 2 (16); Ln = Yb, n = 0 (17)，[Yb(L²)₂(THF)₂] (18)， [Ln(L³)₂(THF)₂･0.25C₆H₁₄] [Ln = Eu (19), Yb (20)]， [{Sm(L³)(μ-I)(THF)}₂] (21) 和 [Sm(L⁵)₂] (22)。 本章亦同時探討二價鑭系配合物15， 18， 20 和 22 作爲還原劑的化學反應特性。 配合物 15 與單質碘反應可得三價銪配合物 [{Eu(L¹)₂(μ-I)}₂] (23)。 配合物 18 與二苯基硫族化合物 PhEEPh (E = S, Se) 反應，可得相對應的三價鐿配合物 [{Yb(L²)₂(μ-EPh)}₂] [E = S (24), Se (25)]。 18 與氯化亞銅反應得到三價鐿配合物 [{Yb(L²)₂(μ-Cl)}₂] (26)。 除此之外，配合物 18 與偶氮苯反應得到雙核配合物 [{Yb(L²)₂}₂(μ-η²:η²-PhNNPh)] (27)， 而 20 與偶氮苯的反應可得單核配合物 [Yb(L³)₂(η²-PhNNPh)･PhMe] (28)。 配合物 22 與二硫化碳的反應得出不對稱偶合配合物 [(L⁵)₂Sm(μ-η³:η²-S₂CSCS)Sm(L⁵)₂] (29)。 / 第四章敍述由胍基配體 L¹ 所衍生的一系列三價鑭系金屬配合物 [Ln(L¹)₃] [Ln = Ce (30), Pr (31), Gd (32), Tb (33), Ho (34), Er (35), Tm (36)] 的合成及其結構。 通過相對應的鑭系金屬三氯化物與 1 反應可得配合物 30-36。 另外， CeCl₃及 LuCl₃與 1 反應亦可合成 [{Ln(L¹)₂(μ-Cl)}₂] [Ln = Ce (37), Lu (38)]。 / 第五章總結了本項研究工作，並對本工作的未來發展作出建議。 / This research work is focused on the coordination chemistry of five closely related guanidinate ligands, namely [(2,6-Me₂C₆H₃N)C(NHPri)(NPri)]⁻ (L¹), [(2,6-Me₂C₆H₃N)C(NHCy)(NCy)]⁻ (L²), [(2,6Me₂C₆H₃N)C{N(SiMe₃)Cy}(NCy)]⁻ (L³), [(2,6Pri₂C₆H₃N)C{N(SiMe₃)₂}(NC₆H₃Pri₂-2,6)]⁻ (L⁴) and [(2,6-Pri₂C₆H₃N)C(NEt₂)(NC₆H₃Pri₂-2,6)]⁻ (L⁵), with divalent chromium and lanthanide metal ions. A series of trivalent lanthanide derivatives of the L¹ ligand were also prepared and structurally characterized in this work. / Chapter 1 gives a brief introduction to the chemistry of metal guanidinate complexes. / Chapter 2 reports on the synthesis, structure and reactivity of chromium(II) complexes derived from the bulky L¹ and L⁴ ligands. Treatment of CrCl₂ with [KL¹･0.5PhMe] (1) afforded the mononuclear Cr(II) bis(guanidinate) complex [Cr(L¹)₂] (3). Reaction of CrCl₂ with [LiL⁴(Et₂O)] (2) resulted in the isolation of ate-complex [Cr(L⁴)(μ-Cl)₂Li(THF)(Et₂O)] (4). Recrystallization of 4 from toluene gave neutral, dimeric [{Cr(L⁴)(μ-Cl)}₂] (5). The reaction chemistry of the Cr(II) complex 3 and 4 was studied. Treatment of 3 with I₂, PhEEPh (E = S, Se, Te), 1-AdN₃ (1-Ad = 1-adamantyl) gave the corresponding mixed-ligand Cr(III) complexes, namely [Cr(L¹)₂I] (6) and [Cr(L¹)₂(EPh)] [E = S (7), Se (8), Te (9)] and Cr(IV) complex [Cr(L¹)₂{N(1-Ad)}] (10). Besides, the reaction of 4 with NaOMe resulted in the isolation of the Cr(II) methoxide-guanidinate complex [{Cr(L⁴)(μ-OMe)}₂] (11). / Chapter 3 deals with the synthesis, structure and reactivity of lanthanide(II) complexes supported by the L¹, L², L³ and L⁵ ligands. Lanthanide(II) guanidinate complexes were prepared by the reactions of an appropriate lanthanide diiodide with the corresponding potassium guanidinate complexes [KL¹･0.5PhMe] (1), [KL²(THF)₀.₅]n (12), KL³ (13) and [KL⁵(THF)₂] (14). Reaction of EuI₂(THF)₂ with 1 gave the homoleptic complex [{Eu(L¹)(μ-L¹)}₂] (15). Metathesis reactions of LnI₂(THF)₂ (Ln = Yb, Eu) with 12 and 13 led to the isolation of [{Ln(L²)(μ-L²)}₂･nC₆H₁₄] [Ln = Eu, n = 2 (16); Ln = Yb, n = 0 (17)], [Yb(L²)₂(THF)₂] (18) and [Ln(L³)₂(THF)₂･0.25C₆H₁₄] [Ln = Eu (19), Yb (20)]. Direct reaction of SmI₂(THF)₂ with 13 yielded the iodide bridged Sm(II) complex [{Sm(L³)(μ-I)(THF)}₂] (21), whilst reaction of SmI₂(THF)₂ with 14 gave homoleptic [Sm(L⁵)₂] (22). The reaction chemistry of 15, 18, 20 and 22 as reducing agents was examined. Oxidation of 15 with I₂ afforded the Eu(III) complex [{Eu(L¹)₂(μ-I)}₂] (23). Reactions of 18 with PhEEPh (E = S, Se) gave the corresponding Yb(III) chalcogenide complexes [{Yb(L²)₂(μ-EPh)}₂] [E = S (24), Se (25)], whilst treatment of 18 with CuCl led to the isolation of [{Yb(L²)₂(μ-Cl)}₂] (26). Besides, addition of complex 18 to PhNNPh yielded binuclear [{Yb(L²)₂}₂(μ-η²:η²-PhNNPh)] (27), whereas treatment of 20 with PhNNPh resulted in the isolation of mononuclear [Yb(L³)₂(η²-PhNNPh)･PhMe] (28). Addition of CS₂ to 22 gave the unsymmetrical coupling product [(L⁵)₂Sm(μ-η³:η²S₂CSCS)Sm(L⁵)₂] (29). / Chapter 4 describes the preparation and structural characterization of lanthanide(III) complexes derived from L¹. A series of homoleptic lanthanide(III) tris(guanidinate) complexes [Ln(L¹)₃] [Ln = Ce (30), Pr (31), Gd (32), Tb (33), Ho (34), Er (35), Tm (36)] were prepared by the reactions of an appropriate LnCl₃ with three molar equivalents of 1. Treatment of CeCl₃ and LuCl₃ with two equivalents of 1 gave the corresponding chloride bridged guanidinate complexes [{Ln(L¹)₂(μ-Cl)}₂] [Ln = Ce (37), Lu (38)]. / Chapter 5 summarizes the findings of this study. A short description on the future prospect of this work will also be given. / 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. / Detailed summary in vernacular field only. / Au, Chi Wai. / Thesis (Ph.D.) Chinese University of Hong Kong, 2014. / Includes bibliographical references. / Abstracts also in Chinese.
| Identifer | oai:union.ndltd.org:cuhk.edu.hk/oai:cuhk-dr:cuhk_1077728 |
| Date | January 2014 |
| Contributors | Au, Chi Wai (author.), Lee, Hung Kay (thesis advisor.), Chinese University of Hong Kong Graduate School. Division of Chemistry, (degree granting institution.) |
| Source Sets | The Chinese University of Hong Kong |
| Language | English, Chinese |
| Detected Language | English |
| Type | Text, bibliography, text |
| Format | electronic resource, electronic resource, remote, 1 online resource (xxi, 275 leaves) : illustrations (some color), computer, online resource |
| 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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