彭旭明臺灣大學：化學研究所王瑞仁Wang, Rui-RenRui-RenWang2007-11-262018-07-102007-11-262018-07-102007http://ntur.lib.ntu.edu.tw//handle/246246/51956摘要 本論文研究的目的為合成及研究不對稱萘啶吡啶胺及其微調四氮配基與相關直線型四核金屬串錯合物。此類型不對稱四氮配基所合成四核鎳金屬串會存在幾何異構物，討論異構化效應對四核鎳金屬串的影響。 (1)合成新型四氮配基分別為萘啶吡啶胺2-α-pyridylamino-1,8-phthyrid-ine簡稱(Hpyany), 2-α-pyrazaylylamino-1,8-naphthyridine (Hpzany)，2-α-picodylamino-1,8-naphthyridine (Hpcany)，這三種不對稱四氮配基是利用鈀金屬催化加成反應，由2-chloro-1,8-naphthyridine 和2-aminopyridine或 2-aminopyrazine或 2-aminopicoline反應而得。由單晶結構得知此系列四氮配基透過胺基的氫原子及萘啶的氮原子產生氫鍵，萘啶和吡啶則產生pi-pi interaction (2) Hpyany所合成四核鎳金屬串錯合物可能會存在四種幾何異構物，分別為(4,0)、(3,1)、(2,2-cis)及(2,2-trans)。錯合物[Ni4(pyany)4(NCS)2]2+主要的異構物為(4,0)及(3,1)構型，由實驗上可以成功的把(4,0)分離，另外以pyrazine取代吡啶為微調四氮配基(Hpzany)，此四氮配基所合成的四核鎳金屬串[Ni4(pzany)4(Cl)2]n+ (n = 1,0)則可成功的分離及得到(4,0)，(3,1)及(2,2-cis)異構物。在四核鎳金屬串電化學分析研究，此金屬串可能存在不同的氧化態，表示方式如[Ni4(pzany)4X2]n+ (n = 0, 1, 2)，當其構型為(4,0)及(3,1)時則四核鎳金屬串為還原一個電子的混價(mixed-valence)錯合物，(2,2-cis)構型為還原兩個電子的混價錯合物，得知異構物之效應。量測[Ni4(pyany)4(NCS)2]2+磁性性質，兩端的鎳為高自旋，兩端自旋狀態為S = 1，存在一反鐵磁J = –65 cm-1，[Ni4(pyany)4(NCS)2] +當還原一個電子在雙核鎳位置時其雙核鎳自旋狀態為S = 3/2，兩組自旋組態為S = 3/2, 1，兩端自旋偶合作用使反鐵磁增強變為J = –83 cm-1。 (4)合成一系列的磺醯胺四氮配基(N-(-)camdapa)、(H2Tsdapa)、(H2Msdapa)，利用此類型配基與萘啶吡啶胺進行混配基的四核鎳金屬串合成，可以得到還原一個電子的四核鎳金屬串，磺醯胺是強拉電子基及立体效應關係使此類型四核鎳金屬串一邊並未有軸向配基且鎳為高自旋狀態，還原一個電子的雙核鎳其自旋狀態為S = 3/2，反鐵磁性為J = -89 cm-1。The goal of this thesis is to study isomer effect to the influence of the metal string complexes. Here we presented the design and preparation of new unsymmetrical tetradentate ligands and the investigation of their linear tetranickel string complexes. X-ray structures, electrochemistry and magnetism of the linear tetranickel string complexes were studied. (1) Three new ligands, 2-α-pyridylamino-1,8-naphthyridine (Hpyany), 2-α-pyrazaylylamino-1,8-naphthyridine (Hpzany), 2-α-picodylamino-1,8-naphthyridine (Hpcany), were synthesized by the palladium-catalyzed cross-coupling of 2-chloro-1,8-naphthyridine with the corresponding amine. The crystal structures of Hpyany, Hpzany and Hpcany were studied, and extensive hydrogen bonding between the amindo group and nitrogen atoms of naphthyridine and pi-pi interaction between pyridine and naphthyridine rings were observed. (2)The linear tetranickel string complexes were synthesized through reacting of ligand with NiCl2. Owing to the asymmetry of the ligands, there are four possible geometrical isomers of the tetranickel string complexes resulting from the orientations of the ligands, abbreviated as (4,0), (3,1) and (2,2-cis) forms. The isomers of tetranickel string complexes were successfully synthesized and isolated. For instance, complex [Ni4(pyany)4(NCS)2]2+ exhibits the major products (4,0) and (3,1) isomers, and [Ni4(pzany)4(Cl)2]n+ (n=1,0) was successfully synthesized and isolated as (4,0)、(3,1) and (2,2-cis) geometric isomers. The electrochemical study showed that different oxidation states are accessible. Through redox reaction, three oxidation states of linear tetranickelstring complexes, eg, complexes with one-electron reduced and two-electron reduced species, [Ni4(L)4X2]n+ (n=0, 1, 2), were successfully obtained and structurally characterized, and their electrochemistry and magnetism were studied. Using our pyrazine-modulated ligand, Hpzany, the tetranickel string [Ni4(pzany)4(Cl)2]n+ (n=2,1,0) were successfully synthesized and isolated as (4,0)、(3,1) and (2,2-cis) geometric isomers. two isomers (4,0) and (3,1) conformation with one-electron reduction occurred on position corresponding to naphthyridine rings; the other is (2,2-cis) form of two-electron reduction products. Therefore, we got further understanding of isomer effect for metal string complexes. (3)The magnetism of linear tetranickel string complexes of different isomers with different oxidation states were studied. The two terminal nickel atoms in [Ni4(pyany)4(NCS)2]2+ existed in high spin state of S = 1 and showed an antiferromagnetic coupling (J = - 36 cm-1 ). However, after one-electron reduction that occurred in the two nickel atoms at the position of naphthyridine rings, the spin state of the two nickel atoms is S =3/2. The antiferromagnetic coupling between two spin states increased to J = - 83cm-1 after one-electron reduction of tetranickel string complexes. (4) A new series of tetranickel string complexes with ligands (H2N-(-)-camdapa), (H2Tsdapa) and (H2Msdapa) were synthesized to study the bulky steric effect. Due to the strong electron-attract effect and bulky steric effect of solfonyl group, mixed-ligand tetranickel string complexes were obtained. The tetranickel string complexes underwent one-electron reduction, producing two complexes with one compound containing an axial ligand Cl– and another no axial ligand. The one-electron reduction occurred in dinickel unit on naphthyridine of compound without axial ligand, generating a strong antiferromagnetic coupling between two spin state of S = 3/2 and S = 1. J = - 89cm-1.第一章：緒論 1 1-1 前言 1 1-2 金屬錯合物相關異構物之簡介 2 1-2-1 有機化合物異構物之類型 2 1-2-2 無機化合物異構物之類型 3 1-2-3 雙核金屬錯合物之幾何異構物 4 1-2-4 直線型三核鈷金屬串對稱與不對稱異構物 7 1-3 金屬–金屬多重鍵理論 8 1-3-1 雙核金屬錯合物 8 1-3-2 過渡金屬三核錯合物之鍵結理論 10 1-3-3 直線型四核金屬串錯合物 13 1-4 配基簡介 13 1-4-1 多吡啶胺(oligo-α-pyridylamine)配基 14 1-4-2 多萘啶胺(oligo-α-naphthyridylamine)配基 14 1-4-3 對稱型吡啶萘啶胺混合配基 15 1-4-4 非對稱型(Unsymmetrical)配基 16 1-4-5 吡啶胺或萘啶胺之衍生或微調配基 16 1-5 萘啶衍生配基及其金屬錯合物簡介 16 1-6 全反向式及直線型金屬錯合物的簡介 18 1-6-1 全反向式金屬錯合物 18 1-6-2 多吡啶胺系列的直線型金屬串錯合物 19 1-6-3 直線型多萘啶胺金屬串錯合物 22 1-6-4 四核鎳金屬串錯合物之簡介 23 1-6-5 直線型萘啶吡啶胺六核金屬串錯合物 24 1-6-6 烯烴配基(Olefin ligand)系列 25 1-6-7 一維無限延展金屬鏈 26 1-7 直線型金屬串錯合物之導電度的量測 26 1-8 研究方向 29 第二章：實驗部分 31 2-1 儀器與試藥 31 2-1-1 試藥 31 2-1-2 儀器 33 2-2 配基之合成 34 2-3 金屬錯合物之合成 41 2-4 萘啶吡啶胺所合成四核鎳金屬串錯合物 43 2-5 微調四氮配基之金屬錯合物 47 2-6 混配基四核鎳金屬鎳錯合物及其相關錯合物 50 第三章：萘啶吡啶胺之配位化學 54 3-1 不對稱萘啶吡啶胺配基及其相關金屬錯合物的研究 54 3-1-1 配基合成發展及討論 54 3-1-2 萘啶吡啶胺配基所合成的金屬錯合物 56 3-2 結構分析與討論 58 3-2-1 萘啶胺相關合成及單晶結構 58 3-2-2 萘啶吡啶胺配基及其微調之共振式 60 3-2-3 不對稱四氮配基配位的模式 63 3-2-4 三種四氮萘啶吡啶相關自由配基結構解析與討論 64 3-3 單核金屬錯合物結構討論 71 3-3-1 單核金屬錯合物結構解析 72 3-3-2 四氮配基和單核金屬錯合物的π-π interaction 之研究 84 3-4 多核金屬錯合物 87 3-5 六核金屬族錯合物 91 3-5-1 [Co6(pyany)4(NCS)4O2] 91 3-5-2 [Cr6(pzany)4Cl6O4] 94 3-6 單核金屬錯合物磁性量測與分析 98 第四章: 四核鎳金屬串及其異構物 104 4-1 直線型四核鎳金屬串錯合物之研究 104 4-1-1 脫氫配基氮的電荷分布及四種異構物的類型 107 4-2 四核鎳金屬串單晶結構解析 108 4-3 微調之四核鎳金屬串錯合物結構解析 121 4-3-1 (4,0)、(3,1)及(2,2-cis)[Ni4(pzany)4(Cl)2]n+異構物 121 4-3-2 (4,0)[Ni4(pcany)4(Cl)2](PF6)2 135 4-4 四核鎳金屬串錯合物之磁性分析 137 4-5 直線型四核鎳金屬串電化學分析 157 4-5-1 三種不對稱四氮配基的電化學比較: 157 4-5-2 四核鎳金屬串錯合物 159 4-5-3 光譜電化學分析 169 4-6 電子吸收光譜 171 4-6-1 三個不對稱四氮配基(Hpyany)、(Hpzany)、(Hpzany) 172 4-6-2 萘啶吡啶胺配基及其直線型四核鎳金屬串錯合物 172 4-6-3 Hpzany 配基及其直線型四核鎳金屬串錯合物 174 4-6-4 (2,2-cis)[Ni4(pzany)4(Cl)2]n+ (n=0,1,2) 175 4-6-5 Hpcany 配基及其直線型四核鎳金屬串錯合物 176 4-7 不對稱四核鎳金屬串之異構物的生成熱ΔHf計算 177 4-8 四核鎳金屬串之異構物性質討論 181 4-8-1 影響異構物生成的因素 181 4-8-2 分析三種金屬串異構物電化學及性質 184 4-8-3 用合成條件來控制四核鎳金屬串之異構物 187 4-8-4 純化異構物的方法 189 第五章: 混配基四核鎳金屬串錯合物 190 5-1 具有光學活性的樟腦磺醯胺四氮配基及其金屬錯合物 191 5-1-1 質子化配基 [(H2(-)camdpda)(H)](ClO4) 192 5-1-2 混配基四核鎳金屬串錯合[Ni4(pyany)2((-)-camdapa)2Cl] 193 5-1-3 混配基四核鎳金屬串錯合物[Ni4(pyany)2(Tsdapa)2Cl] 197 5-1-4 混配基四核鎳金屬串錯合物[Ni4(pyany)2(Msdapa)2Cl] 200 5-2 混配基四核鎳金屬串錯合物之磁性分析 202 5-3 電化學分析 207 5-4 電子吸收光譜 211 5-5 混配基四核鎳金屬串性質分析與結論 214 第六章: 總結 217 6-1 萘啶吡啶胺四氮配基的配位化學 217 6-2 異構化對四核鎳金屬串的影響 218 6-3 混配基四核鎳金屬串的性質 219 6-4 未來展望 219 參考文獻 220 附 錄 225 NMR 光譜 226 快速原子撞擊質譜(FAB) 229 紅外線光譜(IR) 晶體結構圖及晶體數據 235 晶體結構圖及晶體數據 24555607539 bytesapplication/pdfen-US萘啶吡胺胺幾何異構物naphthyridinepyridinegeometric isomerthesishttp://ntur.lib.ntu.edu.tw/bitstream/246246/51956/1/ntu-96-D92223022-1.pdf