臺灣博碩士論文加值系統

摘要
在紫質的衍生物中，碳氮異位紫質已經廣泛的受到注意，其新的衍生物也陸續的被合成且報導出來。研究中，我們將中心金屬鈷離子的碳氮異位紫質做一系列的合成及鑑定，包括：碳氮異位紫質鈷金屬錯合物的合成鑑定和氧化追蹤、六配位錯合物合成、nitrosylation及鈷金屬紫質錯合物與fullerene共結晶。
碳氮異位紫質鈷金屬錯合物的合成鑑定中，我們可以確定CoII(HCTPP) (1)起始物中心金屬鈷為正二價時，為high-spin，順磁性，電子組態為(dxy)2(dxz,dyz)3(dz2)1(dx2-y2)1，屬於四配位的平面結構。在氧化追蹤的過程中，其反應會有二個階段，光譜顯示第一階段為鈷金屬氧化，第二階段則與紫質氧化相關。由於CoII(HCTPP)為四配位的平面結構，所以容易與其他化合物形成五配位或六配位的結構。在五配位及六配位的鈷金屬紫質錯合物中，六配位的CoIII(CTPP)(2-MeIm)2 (3) 由於軸配位基的立體障礙，使得原本共平面的紫質環變成馬鞍型扭曲的非平面結構，且中心金屬為正三價，low-spin，逆磁性，中心金屬的電子組態為(dxy)2(dxz,dyz)4。五配位的鈷金屬紫質錯合物CoII(HCTPP)NO (4) 軸上的M�{N�{O為彎曲型結構，屬於{M(NO)}8平面結構，中心金屬為正二價，low-spin，逆磁性，中心金屬的電子組態為(dxy)2(dxz,dyz)4(dz2)1。而CoIII(CTPPO)NO (5) 軸上的M�{N�{O也是彎曲型結構，但是屬於{M(NO)}7馬鞍型扭曲的非平面結構，中心金屬為為正三價，low-spin，順磁性，中心金屬的電子組態為(dxy)2(dxz,dyz)4。
碳氮異位紫質鈷金屬錯合物與fullerene的共結晶結構中，利用其在溶劑中溶解度的差異得到二種母液養晶，且有二種不同的堆積結構，分別為zigzag及trigonal-cage的型式，化學式分別為C60•CoII(HCTPP)•2C7H8•CH2Cl2 (6)和C60•CoII(HCTPP)•2CH2Cl2 (7)。一般文獻中常見的金屬紫質與C60的堆積為zigzag的結構，而trigonal-cage的結構在文獻中尚未出現過。其中，CoII(HCTPP)與fullerene之間的作用力，也因為堆積結構的不同而有所差異。

Abstract
In the derivatives of the porphyrin system, N-confused porphyrin(NCP) has attracted extensive attention in recent years. In this thesis, we prepared a series of cobalt complexes of N-confused porphyrin and devided the results into four parts including synthesis and oxidation reaction of four coordinated N-confused porphyrin cobalt complex, preparation of six-coordinated cobalt complexes, preparation of nitrosylated cobalt NCP complexes and cocrystallization of cobalt NCP complex with fullerene.
We confirmed that four coordinated and planar starting Co(HCTPP) (1) has a Co+2 metal oxidation state. NMR spectra suggested that it is a high-spin, paramagnetic complex with electronic configuration of (dxy)2(dxz,dyz)3(dz2)1(dx2-y2)1. During the process of oxidation tracing, two steps processes were observed. The first step is the oxidation of Co(II) to Co(III) and the second step is the porphyrin ring oxygenation. Because CoII(HCTPP) is a four coordinated complex, it is easy to form five or six coordinating structure in the presence of coordinating base. Interestingly, in the CoIII(CTPP)(2-MeIm)2 (3), the NCP ring exhibits severe sadde shape distortion, most likely, originated from the steric constrain between the methyl group of 2-MeIm and porphyrin core. We confirmed that the metal centre in CoIII(CTPP)(2-MeIm)2 is low-spin diamagnetic Co(III) ion and the electronic configuration of the metal centre is (dxy)2(dxz,dyz)4. In the case of five-coordination cobalt NCP complex, we have found that CoII (HCTPP)NO (4) exhibits a bent M�{N�{O geometry and belongs to {M(NO)}8 electronic system with a planer porphyrin ring. The metal centre is most likely Co+2, low-spin, diamagnetic and the electronic configuration of the metal centre is (dxy)2(dxz,dyz)4(dz2)1. The oxidation of Co(HCTPP)NO gives CoIII(CTPPO)NO (5). The axial ligand for CoIII(CTPPO)NO is bent M�{N�{O and belongs to {M(NO)}7 electronic structure with a saddling nonplaner porphyrin ring. The metal centre is Co+3, low-spin, paramagnetic and the electronic configuration of the centre metal is (dxy)2 (dxz,dyz)4.
The cocrystallization of cobalt N-confused metalloporphyrin complex and fullerene, utilize its different solubility, obtained two types of crystal structures. The structure with chemical formula of C60•CoII(HCTPP)•2C7H8•CH2Cl2 (6) has a zigzag linear chain orientation while C60•CoII(HCTPP)•2CH2Cl2 (7) exhibits a trigonal-cage structure. The structure of trigonal-cage is not yet appeared in the literature.

目錄
章節
Abstract
摘要
第一章 六配位之碳氮異位紫質鈷金屬錯合物
一、緒論
(一) 紫質化合物
(二) 紫質衍生物
(三) 異位紫質的合成
(四) 異位紫質配位化學與紫質蛋白的關聯
二、實驗
(一) 實驗藥品及其前置處理
(二) 物理性質的測量
(三) 化合物的合成與鑑定
三、實驗結果與討論
四、結論
參考文獻
第二章 一氧化氮之碳氮異位紫質鈷金屬錯合物
一、緒論
(一) 一氧化氮(NO)與紫質蛋白
(二) 一氧化氮與金屬鍵結形式
二、實驗
三、實驗結果與討論
四、結論
參考文獻
第三章 鈷碳氮異位紫質錯合物與C60兩個不同排列的共結晶結構
一、緒論
二、實驗
三、實驗結果與討論
四、結論
參考文獻
第四章 未來工作與展望
參考文獻
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目錄
圖1-1 Porphyrin ring unit
圖1-2 四種紫質大環的變形圖
圖1-3 紫質衍生物分類
圖1-4 異位紫質的結構
圖1-5 carbaporphyrin種類
圖1-6 Carbaporphyrin的寫法定義
圖1-7 單異位紫質的共振式及其高價性
圖1-8 金屬紫質蛋白：(a)葉綠素與(b)維他命B12的結構
圖1-9 CoII(HCTPP) (1) UV-vis 光譜
圖1-10 CoII(HCTPP) (1) 1H NMR 光譜
圖1-11 CoII(HCTPP) (1) 電子組態及軌域分佈(a) low-spin state (b) high-spin state
圖1-12 CoII(HCTPP) (1) EPR 光譜圖(CH2Cl2, 77 K)
圖1-13 CoII(HCTPP) (1) 氧化還原電位CV 光譜
圖1-14 CoII(HCTPP) (1) 晶體結構
圖1-15 CoII(HCTPP) (1) 紫質環平面之鍵長(Å)及鍵角(°)
圖1-16 CoII(HCTPP) (1) 氧化光譜追蹤
圖1-17 CoIII(CTPPO) (2) UV-vis 光譜
圖1-18 CoIII(CTPPO) (2) IR 光譜
圖1-19 CoIII(CTPPO) ESI-MS光譜
圖1-20 CoIII(CTPP)(2-MeIm)2 (3) 與CoIII(CTPP)的UV-vis 光譜比較
圖1-21 CoIII(CTPP)(2-MeIm)2 (3) 1H NMR 光譜
圖1-22 CoIII(CTPP)(2-MeIm)2 (3) 電子組態及軌域分佈
圖1-23 CoIII(CTPP)(2-MeIm)2 (3) 低溫 1H NMR 光譜(DRX500 MHz )
圖1-24 CoIII(CTPP)(2-MeIm)2 (3) 晶體結構
圖1-25 CoIII(CTPP)(2-MeIm)2 (3) 紫質環平面Co(1)含軸配位基之(a)鍵長(Å)
及(b)鍵角(°)
圖1-26 CoIII(CTPP)(2-MeIm)2 (3) 紫質環平面Co(2)含軸配位基之(a)鍵長(Å)
及(b)鍵角(°)
圖1-27 CoIII(CTPP)(2-MeIm)2 (3) 每個原子與平面之距離(a) Co(1) (b) Co(2)
圖1-28 CoIII(CTPP)(2-MeIm)2 (3) 軸配位基的甲基與紫質平面上軸的
夾角及軸配位基上二個甲基之間的夾角(°)
圖1-29 CoIII(CTPP)(2-MeIm)2 (3) 軸配位基偏離紫質平面法線的夾角(°)
圖1-30 CoIII(CTPP)(2-MeIm)2 (3) 軸配位基平面偏離Co�{N(2-MeIm)的夾角(°)
圖2-1 一氧化氮合成酶合成NO之機制
圖2-2 Nitrophorin結構圖
圖2-3 一氧化氮錯合物在{MNO}n系統中，n值與錯合物結構關係
及紅外線光譜範圍
圖2-4 CoII(CTPP)NO (4) UV-vis光譜圖
圖2-5 CoII(CTPP)NO (4) IR光譜圖
圖2-6 CoII(CTPP)NO (4) FAB-MS 光譜圖
圖2-7 CoII(CTPP)NO (4) 1H NMR光譜圖
圖2-8 CoII(CTPP)NO (4) 電子組態及軌域分佈(a) low-spin state
(b) high-spin state
圖2-9 CoII(CTPP)NO (4) 金屬與NO相關分子軌域能接順序
圖2-10 CoII(CTPP)NO(4) 晶體結構
圖2-11 CoII(CTPP)NO (4) 紫質環平面含軸配位基之(a)鍵長(Å)及(b)鍵角(°)
圖2-12 CoII(CTPP)NO (4) 每個原子與平面之距離
圖2-13 CoII(CTPP)NO (4) 軸配位NO與紫質平面M�{N及偏離紫質平面
法線的夾角(°)
圖2-14 在鹵素溶劑中進行nitrosylation (a) CH2Cl2 (b) CH2Br2 (c) CD2Cl2
UV-vis光譜
圖2-15 在鹵素溶劑中進行nitrosylation (a) CH2Cl2 (b) CH2Br2 (c) CD2Cl2 IR光譜
圖2-16 CoII(HCTPP)NO-CH2Cl2 ESI-MS光譜
圖2-17 CoII(HCTPP)NO-CD2Cl2 ESI-MS光譜
圖2-18 CoII(HCTPP)NO-CH2Cl2 1H NMR 光譜圖
圖2-19 CoIII(CTPPO)NO (5) RouteA與Route B及CoIII(CTPPO) (2)
圖2-20 CoIII(CTPPO)NO (5) Route A與Route B IR光譜圖
圖2-21 CoIII(CTPPO)NO (5) EPR光譜圖(CH2Cl2, 77 K)
圖2-22 CoIII(CTPPO)NO (5) 電子組態及軌域分布(a) low-spin state
(b) hight-spin state
圖2-23 CoIII(CTPPO)NO (5) 金屬與NO相關分子軌域能接順序
圖2-24 CoIII(CTPPO)NO (5) 晶體結構
圖2-25 CoIII(CTPPO)NO (5) 紫質環平面含軸配位基之(a)鍵長(Å)及(b)鍵角(°)
圖2-26 CoIII(CTPPO)NO (5) 每個原子與平面之距離
圖2-27 CoIII(CTPPO)NO (5) 軸配位NO與紫質平面M�{C及偏離紫質
平面法線的夾角(°)
圖3-1 紫質與fullerenes形成的Z型結構排列
圖3-2 凹面受體類似結構
圖3-3 Reed工作群之紫質與C60共結晶結構
圖3-4 meso位置取代基的紫質與C60鍵結形成共結晶
圖3-5 C60･CoII(HCTPP)･2C7H8･CH2Cl2 (6) 與C60･CoII(HCTPP)･2CH2Cl2 (7)
及CoII(HCTPP)與C60 UV-vis光譜
圖3-6 CoII(HCTPP)與C60 UV-vis光譜(a)加成光譜(b)混合溶液
圖3-7 (a) CoII(HCTPP)與(b) CoII(HCTPP)C60混合溶液的氧化UV-vis光譜
圖3-8 C60･CoII(HCTPP)･2C7H8･CH2Cl2 (6) 與C60･CoII(HCTPP)･2CH2Cl2 (7)
及CoII(HCTPP)與C60 IR光譜比較
圖3-9 C60･CoII(HCTPP)･2C7H8･CH2Cl2 (6)晶體結構
圖3-10 C60･CoII(HCTPP)･2CH2Cl2 (7)晶體結構
圖3-11 C60･2CoII(HCTPP)･2C7H8･CH2Cl2 (6)晶體堆積zigzag結構
圖3-12 化合物6中C60分子與相鄰二個C60的距離(center-to-center)
圖3-13 化合物6中CoII(HCTPP)與C60每種形式的投射圖
圖3-14 (a)化合物6表現的形狀及大小(b)沿著b軸的排列圖示
圖3-15 C60･CoII(HCTPP)･2CH2Cl2 (7)晶體堆積trigonal-cage結構
圖3-16 化合物7中CoII(HCTPP)及C60分子結合的類型
圖3-17 化合物7中單位晶格單一層四周部份的表示
圖3-18 化合物7中CoII(HCTPP)與C60每一種型態的投射圖
圖4-1 CoII(HCTPP)與不同氧化劑反應UV-vis 光譜(a)AgBF4 (b)mCPBA
圖4-2 CoII(HCTPP)與除氧去離子水反應UV-vis 光譜(a)無THF (b)有THF
圖4-3 CoII(HCTPP)與2-methylimidazole 1H NMR 光譜
圖4-4 CoIII(CTPP)(2-MeIm)2氧化UV-vis 光譜
圖4-5 CoII(HCTPP)與RSNO反應(a) UV-vis及(b) IR 光譜
圖4-6 CoII(HCTPP)與RSNO反應ESI-MS 光譜
圖4-7 free base N-confused porphyrin與C60 UV-vis 光譜
附錄
圖1 (CTPPH)H2 UV-vis光譜
圖2 (CTPPH)H2 ESI-MS光譜
圖3 (CTPPH)H2 1H NMR光譜
圖4 (CTPPH)H2 CV氧化還原光譜
圖5 CoII(HCTPP) ESI-MS光譜 4
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目錄
表1-1 Crystal Data and Structure Refinement for CoII(HCTPP) (1) and
CoIII(CTPP)(2-MeIm)2 (3)
表1-2 CoII(HCTPP) (1) 重要鍵長鍵角
表1-3 CoIII(CTPP)(2-MeIm)2 (3) 重要鍵長鍵角
表1-4 六配位金屬紫質錯合物之重要鍵長鍵角
表2-1 {MNO}n系統之五配位一氧化氮金屬紫質錯合物M�{N�{O夾角
及IR吸收位置
表2-2 nitrosylation鈷紫質錯合物IR光譜吸收值
表2-3 Crystal Data and Structure Refinement for CoII(HCTPP)NO (4)
and CoIII(CTPPO)NO (5)
表2-4 CoII(CTPP)NO (4) 重要鍵長鍵角
表2-5 五配位nitrosylation金屬紫質錯合物之重要鍵長鍵角
表2-6 CoIII(CTPPO)NO (5) 重要鍵長鍵角
表2-7 五配位nitrosylation金屬紫質錯合物之重要鍵長鍵角及IR吸收位置
表3-1 Crystal Data and Structure Refinement for
C60･CoII(HCTPP) 2C7H8･CH2Cl2 (6) and C60･CoII(HCTPP)･2CH2Cl2 (7)
表3-2 C60･CoII(HCTPP) 2C7H8･CH2Cl2 (6)及C60･CoII(HCTPP)･2CH2Cl2 (7)
結構參數




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charp 1
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