含N-苯基-N′-氰基-甲咪配位基，2-氨基噻唑或2-氨基噻唑啉金屬化合物之化學

本論文主要利用不對稱甲咪配位基及氨基噻唑配位基與過渡金屬反應，探討無機分子間的超分子作用力，包含了兩個部分。第一部分主要探討含N-苯基-N′-氰基-甲咪(N-Phenyl-N′-cyano-formamidine) 配位基之二價過渡金屬錯合物的化學。以N- 苯基-N′- 氰基- 甲咪 (N-Phenyl-N′-cyano-formamidine) 配位基分別與Co(NO3)2 · 6H2O 或 Cd(NO3)2 · 4H2O 反應，得到錯化合物Co(NO3)2(HPhCNF)2(THF) (HPhCNF = N-Phenyl-N′-cyano-formamidine) ， 1 及化合物 Cd(NO3)2(HPhCNF)2(THF)，2。化合物1與2的中心鎘或鈷金屬分別與兩組對位的N-苯基-N′-氰基- 甲咪的氰基上的氮原子配位，二個雙芽螯合的硝酸根陰離子上的四個氧原子與一個四氫呋喃上的氧原子配位，形成七配位扭曲的雙五角錐的結構，其分子間是利用多種 X-H---O (X = C 及 N) 形式的氫鍵進行堆疊形成三維結構。第二部份主要探討含2-氨基噻唑(2-Aminothiazole，2AT)為配位基與過渡金屬化合物之化學。以2-AT為配位基與AgNO3、AgClO4、Ag2SO4與Zn(OAc)2 · 2H2O反應，可得到化合物[Ag(2AT)2](ClO4)，3、[Ag(2AT)2](NO3)，4、[Ag2(2AT)2(SO4)][Ag2(2AT)2] (SO4)] · 2(CH3OH)， 5 Zn(OAc)2(2AT)2，6。在化合物3與4中銀原子與兩個2-氨基噻唑配位基上的氮配位鍵結，中心金屬銀原子為趨近於直線形而陰離子未與中心金屬配位，而是以多個Ag---O作用力與中心金屬銀連接，而分子間主要利用中性2-氨基噻唑配位基與陰離子上的氧原子藉由C-H···O形式的氫鍵及芳香環間π - π作用力形成超分子結構。化合物 5 非對稱單元中的晶體結構包含了三種獨立分子，分子間包含了多種的作用力，如: (a) Ag---S (b) Ag---O，(c) Ag---Ag，(d) S---S，(e) S---O，(f) O---O，(g) 氫鍵與(h) π – π 等作用力。化合物 6 其中心金屬為五配位的形式，兩個2- 氨基噻唑 (2-Aminothiazole) 配位基以氮原子與鋅金屬鍵結，中心金屬再分別與雙芽螯合及單芽配位基的醋酸與離子上的氧原子配位。其分子間經由配位基胺基上的氮及陰離子上的氧形成N-H---O的氫鍵及配位基與配位基上的S---S作用力形式在空間中進行堆疊。以2-氨基噻唑啉(2-Amino-2-thiazoline)分別與過氯酸或硝酸水溶液反應，得到 [H(2A2T)][ClO4]，7及[H(2A2T)][NO3]，8。化合物7與8其晶體結構為質子化酸2-氨基噻唑啉陽離子與過氯酸根或硝酸根陰離子共結晶的結構，而氫鍵在此兩結構裡扮演著重要的角色。以上八種化合物的單晶結構均以單晶 X-ray 繞射儀鑑定並紀錄之。

關鍵字

二價鈷化合物；超分子作用力；二價鋅化合物；二價鎘化合物；一價銀化合物

並列摘要

This thesis includes two parts discussing the synthesis, structure andintermolecular interactions of metal complexes containing polydentate ligands. Part I. The reactions of the unsymmetrical N-Phenyl-N′-cyano-formamidine (HPhCNF) ligand with Cd(NO3)2 · 4H2O and Co(NO3)2 · 6H2O affordedtwo complexes of the type M(HPhCNF)2(NO3)2(THF), (M = Cd, 1 ; M =Co), 2 which were characterized by single-crystal X-ray diffraction method and elemental analyses.Both the metal center of complexes 1 and 2 adopt pentagonal bipyramidal geometry. The metal atoms were bonded to two nitrogen atoms of cyano group, four chealting nitrate oxygen atoms, and one oxygen atom of THF solvent group. In these two complexes, C-H---O and N-H---O hydrogen bonds were found to link the molecules. Part II. The reactions of 2-aminotkiazole (2-AT) with AgClO4, AgNO3,Ag2SO4, and Zn(OAc)2 · 2H2O afforded four new complexes of the types of [Ag(2AT)2ClO4], 3 [Ag(2AT)2NO3], 4 [Ag2(2AT)2(SO4)][Ag2(2AT)2](SO4)] · 2(CH3OH), 5 and Zn(OAc)2(2AT)2, 6. Their crystal structures were characterized by single-crystal X-ray diffraction method and elementalanalyses. In complexes 3 and 4, the silver metal centers adopt linear geometry that were bonded to two nitrogen atoms of 2-AT. The molecules adopting linear geometry were interlinked through N-H---O hydrogen bonds. Molecules in complexes 5 were linked through extensive Ag---S, Ag---O, Ag---Ag, S---S, S---O, O---O, hydrogen bondings, and π – π staking interactions. In complex 6, the zinc metal centers were bonded to two nitrogen atoms of two different 2-AT groups, one monodentate acetate and one chealting acetate anion, to form a distorted square pyramidal geometry. The molecules were linked through N-H---O hydrogen bonds and S---S interaction. In compounds 7 and 8, the protonated 2-Amino-2-thiazoline cations, [H(2A2T)]+ were interacted with nitrate and perchlorate anions through hydrogen bonds, forming 1-D hydrogen-bonded tapes. The eight complexes were characterized by single-crystal X-ray diffraction method and elemental analyses.

並列關鍵字

Zn(II) complexes ； Ag(I) complexes ； Cd(II) complexes ； Co(II) complexes

參考文獻

1. (a) Fujita, M. Chem. Soc. Rev. 1998, 27, 417. (b) Winpenny, R. E. P.

Res. 2002, 35, 972.

2. (a) Kitagawa, S.; Kitaura, R.; Noro, S. Angew. Chem., Int. Ed. 2004, 43,

Rosseinsky, M. J. J. Am. Chem. Soc. 2004, 126, 6106. (c) Carlucci, L.;

M. J. Angew. Chem., Int. Ed. Engl. 1997, 36, 972.

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含N-苯基-N′-氰基-甲咪配位基，2-氨基噻唑或2-氨基噻唑啉金屬化合物之化學

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