水溶性之雙亞硝基鐵錯合物及Roussin’s Red Esters

Water-soluble Roussin’s Red Esters (RREs) and Dinitrosyl Iron Complexes (DNICs)

楊宛珊(Wan-Shan Yang)

指導教授 ： 廖文峯

國立清華大學/理學院/化學系/碩士(2009年)

摘要

以3,5-dihydroxybenzyl alcohol為monomer之dendron，利用Hawker以及Fre´chet所發表的合成法”convergent methodology”可合成出[G-1]-Br (3)、[G-2]-Br (5) ( [G-1]-Br 為第一代、[G-2]-Br為第二代之poly(benzyl ether) dendron，其focal point為Br原子)，將化合物3或5分別和[K-18-crown-6-ether]2[Fe2S2(NO)4] (6)在THF下反應會生成dinuclear [{Fe(NO)2}9-{Fe(NO)2}9] DNIC ( dinitrosyl iron complex ) [Fe(SR)(NO)2]2 ( R = [G-2] (7) or [G-1]) (10) )。將化合物7和10進一步與不同化合物反應得到的化合物 [Fe(S-[G-2])(Im)(NO)2]-(8a), [Fe(S-[G-2])(SPh)(NO)2]-(8b), [Fe2(μ-S-[G-2])(μ-S)(NO)4]- (9) 與 anti-[Fe(μ-S-[G-1])(NO)2]2-(11)，以IR、UV-Vis、EPR光譜及X-ray單晶繞射解析，得知化合物11為具有delocalized mixed-valence core 的anionic [{Fe(NO)2}9-{Fe(NO)2}10] Roussin’s red ester，與實驗室所發表的結果相符。接著更以胺基酸為配位基合成出水溶性較佳的化合物[Fe(μ-SCys)(NO)2]2(12), [Fe(μ-SCysMe)(NO)2]2(13), [Fe(SCysMe)2(NO)2] (14)，以IR、UV-Vis光譜鑑定，化合物12在水中與L-Cysteine反應可以得到與化合物14同為13-line hyperfine splitting spectra之[H3O+][Fe(SCys)2(NO)2]，但是化合物14在水中則會轉換成化合物13，由EPR silent的光譜及UV-Vis吸收光譜得到證實。

關鍵字

雙亞硝基鐵錯合物

並列摘要

[G-1]-Br (3) and [G-2]-Br (5) ([G-x]-Br stands for x generation dendron with Br at the focal point) can be synthesized from the monomer, 3,5-dihydroxybenzyl alcohol by Hawker and Fre´chet’s ”convergent methodology”. Reaction of compound 3 ( or compound 5 ) and [K-18-crown-6-ether]2[Fe2S2(NO)4] (6) in a 2:1 molar ratio in THF yielded the dinuclear [{Fe(NO)2}9-{Fe(NO)2}9] dinitrosyl iron complex (DNIC) [Fe(SR)(NO)2]2 (R= [G-2] (7) or [G-1] (10) ). Reaction of compound 7 and NaIm (or NaSPh, [PPN][NO2] ) led to the production of [Fe(S-[G-2])(Im)(NO)2]- (8a) (or [Fe(S-[G-2])(SPh)(NO)2]- (8b), [Fe2(μ-S-[G-2])(μ-S)(NO)4]- (9) ). Reaction of compound 10 and NaNSi2(CH3)6 led to the production of anti-[Fe(μ-S-[G-1])(NO)2]2- (11). Complex 8,9 and 11 were characterized by IR、UV-vis、EPR and X-ray diffraction. Complex 11 is best decribed as the anionic [{Fe(NO)2}9-{Fe(NO)2}10] Roussin’s Red Ester with the fully delocalized mixed-valence core. The better water soluble’s complex [Fe(μ-SCys)(NO)2]2 (12), [Fe(μ-SCysMe)(NO)2]2 (13) and [Fe(SCysMe)2(NO)2] (14) were then synthesized. Complex 12 - 14 were characterized by IR、UV-vis. Reaction of complex 12 and excess L-Cysteine in DI-water produces the 13-line hyperfine splitting spectra－[H3O+][Fe(SCys)2(NO)2]. The transformation of complex 14 into complex 13 in DI-water was observed identified with EPR spectroscopy.

並列關鍵字

Roussin’s Red Esters ； Dinitrosyl Iron Complexes

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