本研究主要以已知化合物[Fe4(C3H3N2)4(NO)8] (1)當作起始物,加入酚 基( phenoxide )和亞硝酸鹽( nitrite )合成O, N配位的雙亞硝基鐵錯合物[(C3H3N2)(OPh)Fe(NO)2]- (2)及[(C3H3N2)(NO2)Fe(NO)2]- (3’),並探討其反應性。 化合物[(C3H3N2)(OPh)Fe(NO)2]- (2)的成功合成證實含Tyrosine和Histidine混合配位之protein-bound DNICs存在的可能性。將此化合物2與等當量的thiol或thiolate反應可以置換化合物2上的酚基形成硫和氮配位的DNICs; 硫氮配位的DNICs再多加一當量的thiol或thiolate則會置換掉咪唑基( Imidazolate ),形成兩個硫配位的DNICs。這一系列反應可以清楚說明S/N/O配位基與{Fe(NO)2}的鍵結能力;也間接證實為何生物體中DNICs較多由半胱胺酸當配位基。化合物[(C3H4N2)2(η2-ONO)Fe(NO)2][18-crown-6-ether]2 (3)的成功合成,又是6配位{Fe(NO)2}9 DNIC的另一例子,而其中間產物[(C3H3N2)(NO2)Fe(NO)2]- (3’)在[OPh]-的存在下,可轉換形成化合物2,在EPR光譜上,化合物3’的室溫光譜g值落在2.03附近,這也間接證實了化合物3’的存在。
In this research, reaction of [Fe4(C3H3N2)4(NO)8] (1) with phenoxide and nitrite led to the formation of [(C3H3N2)(OPh)Fe(NO)2]- (2) and [(C3H3N2)(NO2)Fe(NO)2]- (3’), respectively. Synthesis of the anionic {Fe(NO)2}9 [(C3H3N2)(OPh)Fe(NO)2]- (2) supports the existence of protein-bound NHis/OTyr-DNICs. Reaction of complex 2 and thiol or thiolate in 1:1 molar ratio led to the formation of [(C3H3N2)(SPh)Fe(NO)2]- with mixed imidazolate-/thiolate- coordinated ligands. Addition of another 1 equivalent of thiol or thiolate into imidazolate-/thiolate- coordinated DNIC yielded [(SPh)2Fe(NO)2]- . These reactions elucidate the binding ability of {Fe(NO)2} moiety toward thiolate, imidazolate and phenoxide. The non-classical six-coordinated DNIC{Fe(NO)2}9 [(C3H4N2)2(η2-ONO)Fe(NO)2] [18-crown-6-ether]2 (3) was synthesized. The proposed precursor of complex 3, [(C3H3N2)(NO2)Fe(NO)2]- (3’) with EPR g value 2.03, transforms into complex 2 upon addition of 2 equivalent of phenoxide into it.
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