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研究生:蘇昱誠
研究生(外文):Yu-Cheng Su
論文名稱:萘啶吡啶胺剛性配基及其直線型四核鎳金屬串錯合物之合成與研究
論文名稱(外文):Syntheses and Studies of Linear Tetra-Nickel Metal String Complexes with the New Rigid Ligand
指導教授:彭旭明彭旭明引用關係
指導教授(外文):Shie-Ming Peng
口試委員:王志傑金必耀陳俊顯
口試日期:2015-06-17
學位類別:碩士
校院名稱:國立臺灣大學
系所名稱:化學研究所
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:2015
畢業學年度:103
語文別:中文
論文頁數:89
中文關鍵詞:四核鎳金屬串錯合物剛性配基不對稱型配基三氮苯吩偶數核金屬串錯合物
外文關鍵詞:tetra-nickel metal string complexesrigid ligandunsymmetrical ligand1211-triazabenzo[b]phenoxazineeven-numbered metal string complexes
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對於合成更長鏈的金屬串錯合物,多吡啶胺配基會以syn或anti方式來與金屬作配位,影響著金屬串錯合物的產率高低和副產物多寡,設計將配基只能以syn配位方式來反應,用來解決在多核金屬串錯合物會發生的低產率和多副產物之現象。本論文研究目的為合成不對稱剛性四氮配基(Htzbp)及其金屬串錯合物,並與本實驗室王瑞仁學長合成出一系列四氮配基(Hpyany, Hpzany, Hpcany)及其金屬串錯合物做比較和討論。
將Hpyany的萘啶環和吡啶環以氧鍵結,形成一剛性的新型配基。透過硝化反應、氯化反應及cross coupling,合成出Htzbp (1,2,11-triazabenzo[b]phenoxazine)。將此單晶結構與其他不對稱四氮配基單晶做比較。
利用本實驗室獨特的萘燒法,在高溫220 oC下與金屬反應,形成一含四片配基且直線型金屬串錯合物。不對稱配基合成出的金屬串可能具有四種形式,分別為(4,0)、(3,1)、(2,2-cis)及(2,2-trans),將配基修飾一立體障礙較大的官能基,可控制其金屬串錯合物為(4,0)的配位形式。而Htzbp不具有立體障礙的官能基,因此可能具有四種形式的金屬串錯合物。
[Ni4(tzbp)4(NCS)2](NCS) (2)的X-ray單晶繞射分析,四個配基雖然有失序的情況,但Ni(1)-Ni(2) = 2.4063(9) Å、Ni(2)-Ni(3) = 2.4078(9) Å、Ni(3)-Ni(4) = 2.4300(9) Å,為一個不對稱的鍵長長度;藉由電化學可以發現僅有一組可逆氧化還原電位的訊號;磁性分析上,萘啶單元[Ni2]3+電子組態為S = 3/2,Ni(4)為為獨立之高自旋d8電子組態S = 1;可推斷其為(4,0)[Ni4(tzbp)4(NCS)2](NCS)四核鎳金屬串錯合物。


In order to avoid the potential problem of several side products for synthesizing longer metal strings, the syn mode plays a crucial role. Our lab had been successfully synthesized Hdzp ligand (1,9-diazaphenoxazine), which limited the syn coordination mode of oligo-α-pyridylamine ligands by binding their pyridine rings. Here we present the design and preparation of new unsymmetrical tetra-dentate ligand, Htzbp (1,2,11-triazabenzo[b]phenoxazine), which is rigid by binding 1,8-napthyridine and pyridine ring, and the studies of their tetra-nickel string complexes.
A new ligand, 1,2,11-triazabenzo[b]phenoxazine (Htzbp), is synthesized by nitrification, chlorination and the cross-coupling of 2-chloro-3-nitro-1,8-naphthyridine with 2-amnio-3-hydroxypyridine. The single crystal of Htzbp is studied.
The linear tetra-nickel string complexes are synthesized through reacting of ligand with Ni(OAc)2‧4H2O. Because of the unsymmetrical ligand , there are four possible geometrical isomers of the tetra-nickel string complexes from the orientations of the ligands, abbreviated as (4,0), (3,1), (2,2-cis) and (2,2-trans) forms. Lack of the steric hindrance of the bulky functional group, [Ni4(tzbp)4(NCS)2](NCS) (2) could be one of four geometric isomers.
From the experimental results of X-ray crystallography, the four sets of ligand have the disorder situation, we find out that Ni(1)-Ni(2) = 2.4063(9) Å, Ni(2)-Ni(3) = 2.4078(9) Å and Ni(3)-Ni(4) = 2.4300(9) Å are unsymmetrical Ni-Ni bond length. The electrochemical study shows that there is only one set reversible signal, E1/2(oxi) = +0.2683 V and E1/2(red) = -0.1720 V. The magnetism of linear tetra-nickel string complex is studied, after one electron reduction that occurred in the two nickel atoms at the position of naphthyridine rings, the spin state of the two nickel atom is S = 3/2. As the results of those, we suggest that (4,0)[Ni4(tzbp)4(NCS)2](NCS) is obtained.

口試委員會審定書

中文摘要 I
英文摘要 II
第一章 緒論 1
1-1 分子金屬導線 1
1-2 金屬-金屬鍵結理論 5
1-2-1 雙核金屬錯合物 5
1-2-2 三核金屬錯合物 7
1-2-3 四核金屬錯合物 9
1-2-4 六核金屬錯合物 11
1-3 多氮配基簡介 12
1-3-1 多吡啶胺配基 12
1-3-2 多萘啶胺配基 14
1-3-3 吡啶萘啶胺混合配基 14
1-3-4 吡啶胺或萘啶胺之衍生或微調配基萘啶衍生配基金屬錯合物 17
1-4 萘啶衍生配基金屬錯合物 17
1-5 直線型多核金屬串錯合物 19
1-5-1 奇數核直線型金屬串錯合物 21
1-5-2 四核及其他偶數核直線型金屬串錯合物 24
1-6 研究方向 28
第二章 實驗部分 29
2-1 試藥與儀器 29
2-1-1 試藥 29
2-1-2 儀器 31
2-2 配基合成 32
2-3 四核鎳金屬串錯合物合成 37
第三章 萘啶吡啶胺之合成與性質 39
3-1 不對稱萘啶吡啶胺配基 39
3-1-1 配基設計與合成 40
3-1-2 不對稱萘啶吡啶胺配基支配位模式 42
3-1-3 不對稱萘啶吡啶胺配基所合成的金屬串錯合物 44
3-2 結構分析與討論 45
第四章 四核鎳金屬串錯合物 48
4-1 合成 48
4-2 晶體結構分析與討論 48
4-3 磁性量測與分析 53
4-4 電化學分析 59
4-4-1 不對稱四氮配基 59
4-4-2 直線型四核鎳金屬串錯合物 60
4-5 電子吸收光譜 63
4-5-1 不對稱四氮配基 64
4-5-2 不對稱四氮配基(Htzbp)及其四核鎳金屬串錯合物 65
第五章 總結 66
參考文獻 67
附錄 71
NMR光譜 72
ESI - MS & MALDI - MS質譜 75
IR光譜 79
晶體結構及晶體數據 81


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