透過您的圖書館登入
IP:44.222.104.49
  • 學位論文

萘啶吡啶胺及其四核鎳金屬串幾何異構物之合成與研究

Syntheses and Studies of Geometric Isomers of Tetranickel Strings with 2-α-Pyridylamino-1,8-Naphthyridine Ligand

指導教授 : 彭旭明

摘要


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。

關鍵字

萘啶 吡胺胺 幾何異構物

並列摘要


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.

並列關鍵字

naphthyridine pyridine geometric isomer

參考文獻


16. (a) 林正城,國立台灣大學化學研究所博士論文,1996. (b) 郭敬國,國立台灣大學化學研究所博士論文,2006. (c) Kuo, C.-K.; Chang, J.-C.; Yeh, C.-Y.; Lee, G.-H.; Wang, C.-C.; Peng, S.-M. Dalton Trans. 2005, 3696.
36. (a) X. Lopez, M.-Y. Huang, G.-C. Huang, S.-M. Peng, F.-Y. Li, M. Benard, and M.-M. Rohmer. Inorg. Chem. 2006, 45, 9075-9084.(b) 黃明義,台灣大學化學所博士論文,2005。
24. Y.-H. Chen, C.-C. Lee, C.-C. Wang, G.-H. Lee, S.-Y. Lai, F.-Y. Li, H.-Y. Mou and S.-M. Peng, Chem. Commun., 1999, 1667.
37. (a) C.-H. Chien, J.-C. Chang, C.-Y. Yeh, G.-H. Lee, J.-M. Fang, Y. Song, S.-M. Peng, Dalton Trans., 2006, (26),3249.
2. (a) F. A. Cotton., N. F. Curtis , C. B. Harris, B. F. G. Johnson, S. J. Lippard, J. T. Mague, W. R. Robinson, J. S. Wood, Science ,1964, 145, 1305. (b) F. A. Cotton, N. F. Curtis, B. G. Johnson, W. R. Robinson, Inorg. Chem. 1965, 4, 326. (c) F. A. Cotton, C. B. Harris, Inorg. Chem. 1965, 4, 330.

被引用紀錄


張惟程(2017)。具高導電性之非螺旋性三核混金屬(Mo2/M)串錯合物之合成與研究〔博士論文,國立臺灣大學〕。華藝線上圖書館。https://doi.org/10.6342%2fNTU201704222
陳柏蓉(2017)。(1)十一核鎳金屬串與(2)聯苯萘啶胺三核金屬串的異構物之性質探討〔博士論文,國立臺灣大學〕。華藝線上圖書館。https://doi.org/10.6342%2fNTU201701478
林耿民(2016)。微調二吡啶萘啶二胺配基及其直線型多核金屬串分子之合成與研究〔博士論文,國立臺灣大學〕。華藝線上圖書館。https://doi.org/10.6342%2fNTU201610301
李昫鋒(2016)。不對稱對甲基吡啶噻唑胺配基之三核混鉬/鎳異金屬串錯合物之合成與研究〔碩士論文,國立臺灣大學〕。華藝線上圖書館。https://doi.org/10.6342%2fNTU201600829

延伸閱讀