單核、雙核與多核雙亞硝醯基鐵化合物之合成以及反應性探討

Synthesis and Reactivity of Mononuclear, Dinuclear, and Tetranuclear Dinitrosyl Iron Complexes (DNICs)

王正弘(Jheng-Hong Wang)

指導教授 ： 陳建宏

中山醫學大學/健康管理學院/應用化學系碩士班/碩士(2012年)

摘要

本研究合成{Fe(NO)2}9-{Fe(NO)2}9 [Fe(μ-C5H7N2)(NO)2]2 (1)、{Fe(NO)2}9-{Fe(NO)2}10 [(NO)2Fe(μ-C5H7N2)]2- (2)、{Fe(NO)2}10- {Fe(NO)2}10 [(NO)2Fe(μ-C5H7N2)]22- (3)、{Fe(NO)2}9 [(NO)2Fe- (C5H7N2)2]- (4)、{Fe(NO)2}10-{Fe(NO)2}10 [PPh4]2[Fe(μ-C5H7N2)(μ- SPh)(NO)2]2 ([PPh4]5)，並且以IR,UV-vis, CV, XAS, EPR, X-ray單晶繞射鑑定。
由反應性探討中得知complex 1,2,3彼此可利用氧化還原反應互相轉換，並且用CV進一步證實；而complex 4可作為雙牙配位基分別與[(NO)2Fe(TMEDA)I]/[(TMEDA)Fe(NO)2]生成complex 1/2。並且由EPR,NMR得知complex 3為順磁性化合物而[PPh4]5為逆磁性。
另外也合成出{Fe(NO)2}9 tetranuclear [(NO)2Fe(μ- SC3H4SN)]4 (6)並且經由親核性攻擊生成[N,N]配位的{Fe(NO)2}9 monomeric [(NO)2Fe(SC3H4SN)2]- (7)，並且探討其反應性。
希望藉由本研究進一步了解[S,N]與[N,N]配位形式的DNICs，在生物系統中扮演的角色與可能的反應路徑。

關鍵字

一氧化氮 ； 亞硫醯基鐵化合物 ； 順磁性 ； 逆磁性

並列摘要

{Fe(NO)2}9-{Fe(NO)2}9 [Fe(μ-C5H7N2)(NO)2]2 (1), {Fe(NO)2}9- {Fe(NO)2}10 [(NO)2Fe(μ-C5H7N2)]2- (2), {Fe(NO)2}10-{Fe(NO)2}10 [(NO)2Fe(μ-C5H7N2)]22- (3), {Fe(NO)2}9 [(NO)2Fe(C5H7N2)2]- (4), and {Fe(NO)2}10-{Fe(NO)2}10 [PPh4]2[Fe(μ-C5H7N2)(μ-SPh)(NO)2]2 ([PPh4]5) were synthesized and also characterized by IR, UV-vis, CV, XAS, EPR, and single-crystal X-ray diffraction.
The interconversions among complexe 1, 2, and 3 via reduction and oxidation were demonstrated and further confirmed by cyclic voltammograms. Complex 4 serves as a bidentate ligand to integrate the {Fe(NO)2}9/10 moiety of [Fe(TMEDA)(NO)2I]/[(TMEDA)Fe(NO)2] into complex 1/2. However, both electronic structures of complex 3 and 5 are {Fe(NO)2}10-{Fe(NO)2}10, the complex 3 is paramagnetic and the [PPh4]5 is diamagnetic.
In addition, {Fe(NO)2}9 tetranuclear [(NO)2Fe(μ-SC3H4SN)]4 (6) and {Fe(NO)2}9 [(NO)2Fe(SC3H4SN)2]- (7) have been prepared and the reactivity of complex 6 and 7 was also demonstrated.

並列關鍵字

NO ； DNIC ； {Fe(NO)2}9 ； {Fe(NO)2}10

參考文獻

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