{Fe(NO)2}9及{Fe(NO)2}10亞硫醯基鐵化合物之合成與反應性探討

Sythesis and Reactivity of the {Fe(NO)2}9 and {Fe(NO)2}10 Dintrosyl Iron Complexes (DNICs)

何怡潔(Yi-Chieh Ho)

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(2011年)

摘要

利用[Fe(μ-I)(NO)2]2加入各含S / N的配位基做反應，例如：TMEDA、2-mercapto-1-methylimidazole、[NO2]-，分別可以得到五配位的neutral {Fe(NO)2}9 [(TMEDA)Fe(NO)2I] (1)；neutral {Fe(NO)2}9 [(NO)2Fe(SC4H6N2)I] (8)、anionic {Fe(NO)2}9 [(NO)2Fe(SC4H6N2)2][I] (9) 、[PPN][(NO)2Fe(NO2)I] (12)；另外藉由Fe(CO)2(NO)2個別加入等當量的2-mercapto-1-methylimidazole、2-aminothiophenol反應，分別可以得到[Fe2(SC4H5N2)2(NO)4] (10)及[Fe2(μ-SC6H4-o-NH2)2(NO)4] (18)。
而anionic {Fe(NO)2}10 [K-18-crown-6-ether][(NO)2Fe(NC9H6-NH)] (14)、[K- 18-crown-6-ether][(NO)2Fe(NC9H6-O)] (15)、[K-18-crown-6-ether][(NO)2Fe(NC9H6- S)] (16)、[K-18-crown-6-ether][(NO)2Fe(SC6H4-o-NH2)] (17)則來自[(TMEDA)Fe (NO)2] (2)與ligands(8-aminoquinoline、8-quinolinol、[K][NC9H6-S]、[K][SC6H4- NH2] )在THF溶劑以及CH3CN溶劑中利用去質子反應(deprotonation)及配位基取代(ligand-exchange)反應而得。
另外本研究也合成出{Fe(NO)2}9-{Fe(NO)2}10的[PPh4][(NO)2Fe(μ-SC6H4-o- NH2)]2 (21)與{Fe(NO)2}10-{Fe(NO)2}10的[PPh4]2[(NO)2Fe(μ-SC6H4-o-NH2)]2 (19)；並且利用各種不同的氧化還原劑如Cp2FePF6、Cp2Co等了解{Fe(NO)2}10與{Fe(NO)2}9之間可以相互轉換生成。且利用親核物質[PPh4][SC6H4-o-NH2]與Rossuin’s Red Esters complex 18行thiolate-bridged cleavage反應，生成anionic {Fe(NO)2}9的DNIC [PPh4][(NO)2Fe(SC6H4-o-NH2)2] (20)。而所有的化合物都藉由IR的吸收位置、電子吸收光譜(UV/VIS spectra)、X-ray單晶繞射的結果證實之結構。
希望藉由本研究的反應與化合物的化學特性，期望進一步了解low- molecular-weight DNICs 在生物系統中可能扮演的角色及其轉換途徑。

關鍵字

一氧化氮 ； 亞硫醯基鐵化合物 ； 鐵化合物

並列摘要

Reaction of complex [Fe(μ-I)(NO)2]2 with thiolates or nitrogen-containing ligands such as TMEDA, 2-mercapto-1-methylimidazole, and [NO2]-, led to the formation of neutral five-coordinate {Fe(NO)2}9 [(TMEDA)Fe(NO)2I] (1), neutral four-coordinate {Fe(NO)2}9[(NO)2Fe(SC4H6N2)I] (8), and anionic four-coordinate [(NO)2Fe(SC4H6N2)2][I] (9), [PPN][(NO)2 Fe(NO2)I] (12). In addition, reaction of complex Fe(CO)2(NO)2 with 2-mercapto-1-methylimidazole and 2-aminothiophenol , respectively, afforded dimeric DNICs [Fe2(SC4H5N2)2(NO)4] (10) and [Fe2(μ-SC6H4- o-NH2)2(NO)4] (18).
Besides, a series of anionic {Fe(NO)2}10 DNICs containg [N,NH]/[N,O]/[N,S] ligations ([K-18-crown-6-ether][(NO)2Fe(NC9H6-NH)] (14), [K-18-crown-6-ether] [(NO)2Fe(NC9H6-O)] (15), [K-18-crown-6-ether][(NO)2Fe(NC9H6-S)] (16), and [K- 18-crown-6-ether][(NO)2Fe(SC6H4-o-NH2)] (17) ) were synthesized successfully by using [(TMEDA)Fe(NO)2] (2) as the excellent {Fe(NO)2}10 donor reagent.
In addition, {Fe(NO)2}9-{Fe(NO)2}10 [PPh4][(NO)2Fe(μ-SC6H4 -o-NH2)]2 (21), {Fe(NO)2}10-{Fe(NO)2}10 [PPh4]2[(NO)2Fe(μ-SC6H4-o-NH2)]2 (19), and complex 18 , have been prepared and the interconverison between these monomeric and dimeric DNICs 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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