Title

微調不對稱苯胺吡啶胺萘啶配基及其直線型五核鎳金屬串錯合物之合成與研究

Translated Titles

Syntheses and Studies of Linear Pentanickel Metal-String Complexes with the Fine-tune of Unsymmetrical 2-phenylamino-7-(α-pyridylamino)-1,8-naphthyridine Ligand

DOI

10.6342/NTU201600813

Authors

陳冠廷

Key Words

金屬串 ; 苯胺 ; 微調配基 ; metal string

PublicationName

臺灣大學化學研究所學位論文

Volume or Term/Year and Month of Publication

2016年

Academic Degree Category

碩士

Advisor

彭旭明

Content Language

繁體中文

Chinese Abstract

本論文研究目標以微調配基方式,將不對稱苯胺吡啶胺萘啶配基上修飾一苯基於吡啶之meta位置,合成配基2-phenylamino-7-(5-phenylpyridylamino)-1,8-naphthyridine (簡稱H2phaphpany),再以此配基合成新型五核鎳金屬串錯合物,進行結構分析、磁性、電化學之探討。 於高溫萘燒反應條件下,使用H2phaphpany配基與不同鎳金屬鹽類起始物,可成功得到不同構型之五核鎳金屬串錯合物(2,2)-trans [Ni5(μ5-phaphpany)4(NCS)2]、(3,1)-[Ni5(μ5-phaphpany)4Cl](PF6)、(2,2)-cis [Ni5(μ5-phaphpany)4](PF6)2。 由X-ray單晶繞射解析可知,三種五核鎳金屬串錯合物皆為不同構型,其中(2,2)-trans form為兩端皆有軸向配基;(3,1) form只有一端接上;而(2,2)-cis form則為無軸向配基之五核鎳金屬串錯合物。在鎳-氮鍵長方面,S = 0之金屬鎳離子的鎳-氮距離約為1.9 Å;S = 1之金屬鎳離子的鎳-氮距離大約為2.1 Å,皆分別與文獻中低自旋及高自旋組態之鎳-氮距離相符。磁性量測結果顯示,(2,2)-trans form之金屬串為反鐵磁性,(3,1) form則為順磁性,在300 K時,μeff 值分別為4.03 B.M.及3.33 B.M.。另外,(2,2)-cis form之金屬串我們預期為逆磁性物質。電化學方面,本實驗合成之五核鎳金屬串錯合物與未修飾苯基之五核鎳金屬串錯合物相比,在氧化還原電位上彼此間並無太大差異。

English Abstract

The aim of this thesis is to modify the unsymmetrical H2phapany ligand, replacing the meta-position hydrogen atom of phenyl group. The fine-tuned ligand, H2phaphpany, was synthesized and used to synthesize new type of pentanickel metal-string complexes. Then we investigated their structural characterizations, magnetic properties, electrochemistry and UV spectra. By using different metal salt precursors with H2phaphpany ligand at high temperature, different isomeric forms of pentanickel complexes, (2,2)-trans[Ni5(μ5-phaphpany)4(NCS)2], (3,1)-[Ni5(μ5-phaphpany)4Cl](PF6) and (2,2)-cis [Ni5(μ5-phaphpany)4](PF6)2 could be synthesized successfully. The X-ray structures show that the three pentanickel complexes are different isomeric forms where (2,2)-trans form present axial ligand at both terminal nickel atoms, (3,1) form is absence of axial ligand at one terminal nickel atom and (2,2)-cis form is absence of axial ligand at both terminal nickel atoms. In the Ni-N bond distances, low spin Ni(Ⅱ) ions display short Ni-N(~1.9 Å) bond distances, and high spin Ni(Ⅱ) ions display long Ni-N bond distances(~2.1 Å). Both of them are consistent with a low spin Ni(Ⅱ) and high spin Ni(Ⅱ) configuration in nickel metal-string complexes. The magnetic susceptibility shows that (2,2)-trans form exhibits antiferromagnetic interaction, (3,1) form exhibits paramagnetic behavior and (2,2)-cis form is expected to exhibit diamagnetic behavior. In the study of cyclic voltammetry, both two complexes comparing with pentanickel complexes of unmodified phenyl group show no significant difference.

Topic Category 基礎與應用科學 > 化學
理學院 > 化學研究所
Reference
  1. 1. F. Wöhler, Ann. Phys., 1828, 12, 253-256.
    連結:
  2. 2. A. Z. Werner, Anorg. Chem., 1893, 3, 267-330.
    連結:
  3. 3. (a) F. A. Cotton, N. F. Curtis, C. B. Harris, B. G. Johnson, S. J. Lippard, J. T. Mague, W. R. Robinson and J. S. Wood, Science., 1964, 145, 1305-1307. (b) F. A. Cotton, N. F. Curtis, B. G. Johnson and W. R. Robinson, Inorg. Chem., 1965, 4, 326-330. (c) F. A. Cotton, C. B. Harris, Inorg. Chem., 1965, 4, 330-333.
    連結:
  4. 6. (a) S.-J. Shieh, C.-C. Chou, G.-H. Lee, C.-C.Wang and S.-M. Peng, Angew. Chem. Int. Ed. Engl., 1997, 36, 56-59. (b) C.-C. Wang, W.-C. Lo, C.-C. Chou, G.-H. Lee, J.-M. Chen and S.-M. Peng, Inorg. Chem., 1998, 37, 4059-4065.
    連結:
  5. 7. H.-C. Chang, J.-T. Li, C.-C. Wang, T.-W. Lin, H.-C. Lee, G.-H. Lee and S.-M. Peng, Eur. J. Inorg. Chem., 1999, 1243-1251.
    連結:
  6. 8. S.-Y. Lai, T.-W. Lin, Y.-H. Chen, C.-C. Wang, G.-H. Lee, M.-H. Yang, M.-K. Leung and S.-M. Peng, J. Am. Chem. Soc., 1999, 121, 250-251.
    連結:
  7. 9. Y.-H. Chen, C.-C. Lee, C.-C. Wang, G.-H. Lee, S.-Y. Lai, F.-Y. Li, C.-Y. Mou and S.-M. Peng, Chem Commun., 1999, 17, 1667-1668.
    連結:
  8. 11. A. Aviram and M. Ratner, Chem. Phys. Lett., 1974, 29, 277-283.
    連結:
  9. 15. (a) C.-H. Chen, J.-C. Chang, C.Y. Yeh, G.-H. Lee, J.-M. Fang and S.-M. Peng, Dalton Trans., 2006, 35, 2106-2113.(b) C.-H. Chen, J.-C. Chang, C.-Y. Yeh, G.-H. Lee, J.-M. Fang, Y. Song and S.-M. Peng, Dalton Trans., 2006, 35, 2349-3256.
    連結:
  10. 16. 楊景鈞,國立台灣大學化學研究所博士論文,2014.
    連結:
  11. 17. 趙世烜,國立台灣大學化學研究所碩士論文,2006.
    連結:
  12. 19. 邱梅君,國立台灣大學化學研究所碩士論文,2006.
    連結:
  13. 20. C.-C. Young, P.-C. Liu, Y.-J. Hsu, G.-H. Lee, C.-H. Chen and S.-M. Peng, Eur. J. Inorg. Chem., 2013, 263-268.
    連結:
  14. 21. 洪偉捷,國立台灣大學化學研究所碩士論文,2012.
    連結:
  15. 22. 簡智賢,國立台灣大學化學研究所博士論文,2005.
    連結:
  16. 24. 黃明義,國立台灣大學化學研究所博士論文,2006.
    連結:
  17. 25. 陳治棻,國立台灣大學化學研究所碩士論文,2006.
    連結:
  18. 26. 林依潔,國立台灣大學化學研究所碩士論文,2015.
    連結:
  19. 4. E.-C. Yan, M.-C. Cheng, M.-S. Tsai and S.-M. Peng, J. Chem. Soc., Chem.Commun., 1994, 20, 2377-2378.
  20. 5. J.-T. Sheu, C.-C.Lin, I. Chao, C.-C.Wang and S.-M. Peng, Chem Commun., 1996, 7, 315-316.
  21. 10. S.-M. Peng, C.-C. Wang, Y.-L. Chiang, Y.-H. Chen, F.-Y. Li, C.-Y. Mou and M.-K. Leung, J. Mag. Mag. Mater., 2000, 209, 80-83.
  22. 12. S. Wagaw and S. L. Buchwald, J. Org. Chem., 1996, 61, 7240-7241
  23. 13. (a) C.-H. Chien, J.-C. Chang, C.-Y. Yen, G.-H. Lee, J.-M. Fang and S.-M. Peng, Dalton Trans., 2006, 17, 2106-2113. (b). S.-A. Hua, I. P.-C. Liu, H. Hasanov, G.-C. Huang, R. H. Ismayilov, C.-L. Chiu, C.-Y. Yeh, G.-H. Lee and S.-M. Peng, Dalton Trans., 2010, 39, 3890-3896.
  24. 14. R. H. Ismayilov, W.-Z. Wang, G.-H. Lee, C.-Y. Yeh, S.-A. Hua, Y. Song, M.-M. Rohmer, M. Benard and S.-M. Peng, Angew. Chem. Int. Ed., 2011, 50, 2045-2048.
  25. 18. (a) J. F. Berry, F. A. Cotton, T. Lu, C.A. Murillo and X. Wang, Inorg. Chem., 2003, 42, 3595-3601.(b) J. F. Berry, F. A. Cotton, T. Lu and C.A. Murillo X., Inorg. Chem., 2003, 42, 4425-4430.(c) J. F. Berry, F. A. Cotton, P. Lei, T. Lu and C.A. Murillo, Inorg. Chem., 2003, 42, 3534-3539.(d) J. F. Berry, F. A. Cotton, C. S. Fewox, T. Lu, C.A. Murillo and X. Wang, Dalton Trans., 2004, 33, 2297-2302.(e)C.-X. Yin, J. Su, F.-J. Huo, R. H. Ismayilov, E.-Z. Wang, G.-H. Lee, C.-Y. Yeh and S.-M. Peng, J. Coord. Chem., 2009, 62, 2974-2982.
  26. 23. 林子偉,國立台灣大學化學研究所碩士論文,1998.