EPR, UV-Vis, IR, and x-ray demonstration of the anionic dimeric dinitrosyl iron complex [(NO)2Fe(μ-StBu)2Fe(NO)2]-:: Relevance to the products of nitrosylation of cytosolic and mitochondrial aconitases, and high-potential iron proteins
EPR, UV-Vis, IR, and x-ray demonstration of the anionic dimeric dinitrosyl iron complex [(NO)2Fe(μ-StBu)2Fe(NO)2]-:: Relevance to the products of nitrosylation of cytosolic and mitochondrial aconitases, and high-potential iron proteins
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DOI：
10.1021/ja0751375
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发表时间：
2007-10-24
影响因子：
15
通讯作者：
Liaw, Wen-Feng
中科院分区：
文献类型：
--
作者：
Tsou, Chih-Chin;Lu, Tsai-Te;Liaw, Wen-Feng
配合物[（NO）（2）Fe（S-（BU）-B-t）（2）]（-）（3-Na）和[Fe-2（（SBu）-S-/直角-Bu-t）（2）（NO）（4）]（1）在质子溶剂MeOH中处于动态平衡。随后将等量的二茂钴加入到配合物3-Na和1的甲醇溶液混合物中，形成了完全离域的混合价[Fe（（/直角）-LS-Bu-t）（NO）（2）]（2）-（2），通过IR，UV-vis，EPR，SQUID和单晶X-射线衍射对其进行了表征。复合物2的EPR谱显示在g垂直于= 2.009，g平行于= 1.965（77 K）处的轴向信号和在g = 1.998（298 K）处的各向同性信号，与从乌头酸酶的亚硝基化和含HiPIP的蛋白质结合的DNIC的还原获得的二亚硝酰铁复合物（DNIC）/乌头酸酶的还原的EPR谱相同，表明乌头酸酶/HiPIP的[4Fe-4S]（2+）簇被亚硝基化以产生单体和二聚体DNIC的混合物。
Complexes [(NO)(2)Fe(S-(BU)-B-t)(2)](-) (3-Na) and [Fe-2((SBu)-S-/right angle-Bu-t)(2)(NO)(4)] (1) are in dynamic equilibrium in the protic solvent MeOH. The subsequent addition of the equivalent of cobaltocene into the MeOH solution mixture of complexes 3-Na and 1 led to the formation of the fully delocalized mixed-valence [Fe((/right angle)-LS-Bu-t)(NO)(2)](2)- (2) characterized by IR, UV-vis, EPR, SQUID, and single-crystal X-ray diffraction. The EPR spectrum of complex 2 displaying an axial signal at g perpendicular to = 2.009, g parallel to = 1.965 (77 K) and an isotropic signal at g = 1.998 (298 K), identical to the EPR spectra of reduction of dinitrosyl iron complex (DNIC)/aconitase obtained from nitrosylation of aconitase and reduction of HiPIP-containing protein-bound DNIC, suggests that the [4Fe-4S](2+) clusters of aconitase/HiPIP were nitrosylated to produce a mixture of the monomeric and dimeric DNICs.