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  • 學位論文

含二-(吡啶)或二-(嘧啶)配位基 與過渡金屬化合物之研究

Chemistry of Transition Metal Complexes Containing Dipyridyl or Dipyrimidyl Lignads

指導教授 : 陳志德

摘要


經由過渡金屬化合物CuCl2, CuBr2 及Cu(ClO4)2 與配位基 N,N'-bis(2-pyridinyl)-1,4-benzenedicarboxamide (L1) 的反應,得到了 Cu2Cl4(L1)(DMSO)2 · 2DMSO, 2, Cu2Br4(L1)(DMSO)2 · 2DMSO, 3 與[Cu2(L1)(DMSO)6](ClO4)4 · 2DMSO, 4 以 HgCl2, HgBr2 及 Cd(NO3)2, 與配位基N,N'-bis(2-pyrimidinyl)-1,4-benzenedicarboxamide (L2) 的反應得到了Hg2(L2)Cl4, 7, {Hg(L2)Br2 · H2O}∞, 8, {[Cd(L2)(NO3)2] · 2DMF}∞, 9 此六個錯化合物的構造均已利用 X-ray 鑑定之。化合物 2 和 3 形成雙核的金屬化合物,而分子間 是經由 N-H---O 和 C-H---X (X = Cl, Br) 的氫鍵作用力所連接起 來。錯化合物 4 亦為雙核的金屬錯化合物,而分子間是經由 N-H---O 和 C-H---O 的氫鍵作用力所連接起來。化合物 7 形成雙 核的金屬錯化合物,而每個分子是經由 N-H---Cl 和 C-H---Cl 的氫 鍵作用力所連接起來。錯化合物 8 形成鋸齒狀的長鏈,每條長練 是經由 C-H---Br 和 C-H---O 的氫鍵作用力所連接起來。錯化合物 9 形成鋸齒狀的長鏈,每條長練是經由 N-H---O 和 C-H---O的氫 鍵作用力所連接起來。

並列摘要


A series of the transition metal complexes Cu2Cl4(L1)(DMSO)2 · 2DMSO, 2, Cu2Br4(L1)(DMSO)2 · 2DMSO, 3, [Cu2(L1)(DMSO)6](ClO4)4 · 2DMSO, 4, Hg2(L2)Cl4, 7, {Hg(L2)Br2 · H2O}∞, 8, and {[Cd(L2)(NO3)2] · 2DMF}∞, 9, where L1 = N,N'-bis(2-pyridinyl)-1,4-benzenedicarboxamide; L2 = N,N'-bis- (2-pyrimidinyl)-1,4-benzenedicarboxamide, have been prepared by the reactions of transition metal compounds CuCl2, CuBr2, Cu(ClO4)2, HgCl2, HgBr2, and Cd(NO3)2 with L1 and L2. All the complexes have been structurally characterized by X-ray crystallography, confirming that 2 - 4 and 7 are binuclear complexes, and 8 - 9 are coordination polymers. Complexes 2 and 3 form binuclear complexes which are interlinked through a series of S---S interactions and C-H---X (X = Cl, Br) hydrogen bonds. Complex 4 forms binuclear complexes which are interlinked through a series of N-H---O and C-H---O hydrogen bonds. Complex 7 forms binuclear complexes which are interlinked through a series of N-H---Cl and C-H---Cl hydrogen bonds. Complexes 8 and 9 form zigzag chains, where the molecules of complex 8 are interlinked by C-H---Br hydrogen bonds and those of complex 9 are interlinked by a series of N-H---O and C-H---O hydrogen bonds.

參考文獻


1. (a) Desiraju, G. R. Angew. Chem., Int. Ed. Engl. 1995, 34, 2311. (b)
Desiraju, G. R. Chem. Commun. 1997, 1475. (c) Lehn, J. M.
Hoskins, B. F.; Lieu, J. Supramolecular Architecture; ACS
Angew. Chem., Int. Ed. 1998, 37, 1460. (c) Yaghi, O. M.; Li, H.;
Am. Chem. Soc. 1999, 121, 2599. (e) Aakeröy, C. B.; Seddon, K. R.

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