本文的第一部分為雙鉻五重鍵錯合物Cr2[μ-η2-HC(N-2,6-Et2C6-
H3)2]2 (1a)對雙氮基脒、炔類及一氧化氮的反應性研究。將錯合物1a與不同立體阻礙之去質子化的雙氮基脒及冠醚進行反應，可得到M2L6燈籠型雙鉻五重鍵錯合物[K(18-crown-6 ether)(THF)2]{Cr2[μ-η2-HC(N-4-CH3C6H4)2][μ-η2-HC(N-2,6-Et2C6H3)2]2}□(1)、[K(18-crown-6 ether)(THF)]{Cr2[μ-η2-HC(N-3,5-Me2C6H3)2][μ-η2-HC(N-2,6-Et2C6H3)2]2}(2)及[K(benzo-15-crown-5 ether)2]{Cr2[μ-η2-HC(N-2,6-Et2C6H3)2]3}(3)。錯合物1、2及3具有極短的雙鉻五重鍵，鍵長約為1.74 Å且具C2v(1和2)及D3(3)的對稱性。除此之外，將錯合物1a與3□己炔及二苯乙炔等炔類進行反應，可得到M2L6燈籠型雙鉻四重鍵錯合物(μ-η1：η1-EtCCEt)Cr2[μ-η2-HC(N-2,6-Et2C6H3)2]2 (4)及(μ-η1：η1-PhCCPh)Cr2[μ-η2-HC(N-2,6-Et2C6H3)2]2 (5)等。炔類配基呈現約50°的扭轉角度橋接在雙鉻之間。如此的扭轉結構是源自於第二級Jahn Teller效應，使得炔類分子以一個特殊的扭轉角度與雙鉻五重鍵進行配位。將過量一氧化氮通入錯合物1a、4及Cr2[μ-η2-HC(N-2,6-Et2C6H3)2]3 (2a)，分別得到單核鉻-亞硝基錯合物(η1-NO)2Cr[η2-HC(N-
2,6-Et2C6H3)2]2 (6)、雙核鉻錯合物(μ-η1-ONO)2[Cr(η1-NO)2]2[μ-η2-HC(N-2,6-Et2C6H3)2]2 (7)及[Cr(η1-NO)]2[μ-η2-HC(N-2,6-Et2C6H3)2]3 (8)。錯合物6-8配位著不同數目的亞硝基，但所有的亞硝基皆以直線型的方式配位至鉻金屬上。而錯合物7-8其雙鉻之間的距離分別為3.081(1) 及3.022(1) Å，故雙鉻之間失去了鍵結。值得注意的是錯合物7具有兩個以其中一個氧端橋接在雙鉻之間的亞硝酸基，推論是一氧化氮在鉻金屬存在時經由歧化反應(disproportionation)產生亞硝酸基。
本文的第二部分，是有關鋯、釩及錳之低配位錯合物的合成與特性。將四氯化鋯與去質子化的胍配基[μ-η2-(iPr2N)C(N-2,6-iPr2C6H3)2]Li(THF)在甲苯溶液中反應且由四氫呋喃再結晶，得到了[μ-η2-
(iPr2N)C(N-2,6-iPr2C6H3)2]ZrCl3(THF) (9)。經X-ray分析得知錯合物9為一扭曲的八面體構形。將錯合物9與氫化鋁鋰反應，得到兩種雙核鋯之胍配基錯合物(μ-Cl){μ-Cl[Li(THF)]}Zr2[η2-(iPr2N)C(N-2,6-iPr2(C6H3)2]2 (10a)與{μ-Cl[Li(THF)]}2Zr2[η2-(iPr2N)C(N-2,6-iPr2C6H3)2]2(10b)。以VCl3(THF)3與{HC[C(CH3)N-2,4,6-iPr3C6H2]2}Li(THF)反應可得到{HC[C(CH3)N-2,4,6-iPr3C6H2]2}VCl2。再以KC8將{HC[C(CH3)N-2,4,6-iPr3C6H2]2}VCl2還原，還原後可得到雙核釩(II)錯合物(μ-Cl)2V2{HC[C(CH3)N-2,4,6-iPr3C6H2]2}2(THF)2 (11)。具有兩個氯原子橋接兩個釩原子，每個釩原子具有一扭曲的金字塔構形(square pyramidal geometry)。在錳之低配位錯合物的合成，將具較大立體阻礙的去質子化β-二酮亞胺配基{HC[C(tBu)N-2,4,6-iPr3C6H2]2}Li(THF)與二氯化錳反應，可得到一單核四面體的錳(II)錯合物{HC[C(tBu)N-2,4,6-iPr3C6H2]2}MnCl(THF) (12)。

中文摘要...................................................I
Abstract.................................................III
謝誌.......................................................V
目錄......................................................VI
圖目錄....................................................IX
流程圖目錄................................................XI
表目錄...................................................XII
第一章 緒論................................................1
1. 金屬-金屬多重鍵的發展...................................1
2. 一氧化氮(NO)的物性與化性 ..............................10
第二章 雙鉻金屬五重鍵錯合物與雙氮基脒配基之反應...........13
2-1.前言. ................................................13
2-2.[K(18-crown-6 ether)(THF)2]{Cr2[μ-η2-HC(N-4-CH3C6H4)2][μ-η2-HC(N-2,6-Et2C6H3)2]2} (1)的合成[PF-430]...........14
2-3.[K(18-crown-6 ether)(THF)]{Cr2[μ-η2-HC(N-3,5-Me2C6H3)2][μ-η2-HC(N-2,6-Et2C6H3)2]2} (2)的合成[PF-441].........16
2-4.[K(benzo-15-crown-5 ether)2]{Cr2[μ-η2-HC(N-2,6-Et2C6H3)2]3} (3)的合成[PF-426]............................18
2-5. 實驗步驟.............................................23
2-5-1. [K(18-crown-6 ether)(THF)2]{Cr2[μ-η2-HC(N-4-CH3C6H4)2][μ-η2-HC(N-2,6-Et2C6H3)2]2} (1)的合成[PF-430].23
2-5-2. [K(18-crown-6 ether)(THF)]{Cr2[μ-η2-HC(N-3,5-Me2C6H3)2][μ-η2-HC(N-2,6-Et2C6H3)2]2} (2)的合成[PF-441].24
2-5-3. [K(benzo-15-crown-5 ether)2]{Cr2[μ-η2-HC(N-2,6-Et2C6H3)2]3}(3)的合成[PF-426].............................25
第三章 雙鉻金屬五重鍵錯合物與炔類之反應..................27
3-1. 前言 ................................................27
3-2. (μ-η1：η1-EtCCEt)Cr2[μ-η2-HC(N-2,6-Et2C6H3)2]2 (4)的合成[PF-373]............................................27
3-3. (μ-η1：η1-PhCCPh)Cr2[μ-η2-HC(N-2,6-Et2C6H3)2]2 (5)的合成 [PF-446]...........................................34
3-4. 實驗步驟.............................................37
3-4-1. (μ-η1：η1-EtCCEt)Cr2[μ-η2-HC(N-2,6-Et2C6H3)2]2 (4)的合成[PF-377].........................................37
3-4-2. (μ-η1：η1-PhCCPh)Cr2[μ-η2-HC(N-2,6-Et2C6H3)2]2 (5)的合成[PF-446].........................................38
第四章 雙鉻金屬多重鍵錯合物與一氧化氮之反應..............39
4-1. 前言 ................................................39
4-2. (η1-NO)2Cr[η2-HC(N-2,6-Et2C6H3)2]2 (6)的合成[PF-373]......................................................39
4-3. (μ-η1-ONO)2[Cr(η1-NO)2]2[μ-η2-HC(N-2,6-Et2C6H3)2]2 (7)的合成 [PF-579]...... ..............................44
4-4. [Cr(η1-NO)]2[μ-η2-HC(N-2,6-Et2C6H3)2]3 (8)的合成[PF-414]......................................................49
4-5. 實驗步驟.............................................51
4-5-1. (η1-NO)2Cr[η2-HC(N-2,6-Et2C6H3)2]2 (6)的合成[PF-373]......................................................51
4-5-2. (μ-η1-ONO)2[Cr(η1-NO)2]2[μ-η2-HC(N-2,6-Et2C6H3)2]2 (7)的合成[PF-579].....................................52
4-5-3. [Cr(η1-NO)]2[μ-η2-HC(N-2,6-Et2C6H3)2]3 (8)的合成[PF-414]..................................................53
第五章 鋯、釩、錳之低配位金屬錯合物的合成...............54
5-1. 前言 ................................................54
5-2. [μ-η2-(iPr2N)C(N-2,6-iPr2C6H3)2]ZrCl3(THF) (9)的合成[PF-189]..................................................54
5-3. (μ-Cl){μ-Cl[Li(THF)2]}Zr2[η2-(iPr2N)C(N-2,6-iPr2C6H3)2]2 (10a)及{μ-Cl[Li(THF)]}2Zr2[η2-(iPr2N)C(N-2,6-iPr2C6H3)2]2 (10b)的合成[PF-308]..........................58
5-4. (μ-Cl)2V2{HC[C(CH3)N-2,4,6-iPr3C6H2]2}2(THF)2 (11)的合成 [PF-61]...............................................62
5-5. {HC[C(tBu)N-2,4,6-iPr3C6H2]2}MnCl(THF) (12)的合成[PF-33].......................................................65
5-6. 實驗步驟.............................................67
5-6-1. [μ-η2-( iPr2N)C(N-2,6-iPr2C6H3)2]ZrCl3(THF) (9)的合成[PF-189]................................................67
5-6-2. {(μ-Cl){μ-Cl[Li(THF)2]}Zr2[η2-(iPr2N)C(N-2,6-iPr2C6H3)2]2 (10a)的合成[PF-308]..........................67
5-6-3. {μ-Cl[Li(THF)]}2Zr2[η2-(iPr2N)C(N-2,6-iPr2C6H3)2]2 (10b)的合成[PF-308].......................................68
5-6-4. (μ-Cl)2V2{HC[C(CH3)N-2,4,6-iPr3C6H2]2}(THF)2 (11)的合成[PF-61]...............................................69
5-6-5. {HC[C(tBu)N-2,4,6-iPr3C6H2]2}MnCl(THF) (12)的合成[PF-33].......................................................69
第六章 實驗儀器與藥品...................................70
6-1.總綱..................................................70
6-2.實驗儀器..............................................70
6-3.實驗溶劑與藥品 .......................................71
參考文獻..................................................85

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