Dinitrosyl iron complexes [E5Fe(NO)2]- (E = S, Se):: A precursor of Roussin's black salt [Fe4E3(NO)7]-
Dinitrosyl iron complexes [E5Fe(NO)2]- (E = S, Se):: A precursor of Roussin's black salt [Fe4E3(NO)7]-
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DOI：
10.1016/j.ica.2006.02.035
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发表时间：
2006-05-15
影响因子：
2.8
通讯作者：
Liaw, Wen-Feng
中科院分区：
文献类型：
--
作者：
Chen, Tai-Nan;Lo, Feng-Chun;Liaw, Wen-Feng
合成了[PPN][Se_5 Fe（NO）（2）]（1）和[K-18-冠-6-醚][S_5 Fe（NO）（2）]（2 '），并通过IR、UV-Vis、EPR、磁化率和X-射线衍射进行了表征。[PPN][Se_5Fe（NO）_21容易与S-8和（RS）（2）（R = C_7H_4SN（5），o-C_6 H_4 NHCOCH_3（6），C_4H_3S（7））发生配体交换，生成[PPN][S_5Fe（NO）（2）]和[PPN][（SR）（2）Fe（NO）（2）]。反应表明，在THF中，分别加入酸HBF_4或氧化剂[Cp_2Fe][BF_4]，[E_5Fe（NO）（2）]（-）（E = Se（3），S（4））可容易地转化为[Fe_4E_3（NO）（7）]（-）。显然，配合物1和2'作为黑色素黑盐3和4的前体。[Se 5 Fe（NO）（2）]（-）的{Fe（NO）2）9核的电子结构最好描述为{Fe+1（-NO）（2）}（9）和{Fe-1（NO+）（2）}（9）的动态共振杂化，并受配体的调节。的调查结果，g = 2.064的EPR信号为1在298 K，暗示，低分子量的DNIC和蛋白质结合的DNIC可能不存在与硒代半胱氨酸残基的蛋白质作为配体，因为蛋白质结合的DNIC和低分子量的DNIC在体外的存在已被其特征在于与特征EPR信号在g = 2.03。此外，暴露于UV-A光的复合物2'处理的人红白血病K562癌细胞大大降低了细胞培养物的存活百分比。(c)2006 Elsevier B. V.保留所有权利。
[PPN][Se5Fe(NO)(2)] (1) and [K-18-crown-6-ether][S5Fe(NO)(2)] (2') were synthesized and characterized by IR, UV-Vis, EPR spectroscopy, magnetic susceptibility, and X-ray structure. [PPN][Se5Fe(NO)21 easily undergoes ligand exchange with S-8 and (RS)(2) (R = C7H4SN (5), o-C6H4NHCOCH3 (6), C4H3S (7)) to form [PPN][S5Fe(NO)(2)] and [PPN][(SR)(2)Fe(NO)(2)]. The reaction displays that [E5Fe(NO)(2)](-) (E = Se (3), S (4)) facilely converts to [Fe4E3(NO)(7)](-) by adding acid HBF4 or oxidant [Cp2Fe][BF4] in THF, respectively. Obviously, complexes 1 and 2' serve as the precursors of the Roussin's black salts 3 and 4. The electronic structure of {Fe(NO)2)9 core of [Se5Fe(NO)(2)](-) is best described as a dynamic resonance hybrid of {Fe+1(-NO)(2)}(9) and {Fe-1(NO+)(2)}(9) modulated by the coordinated ligands. The findings, EPR signal of g = 2.064 for 1 at 298 K, implicate that the low-molecular-weight DNICs and protein-bound DNICs may not exist with selenocysteine residues of proteins as ligands, since the existence of protein-bound DNICs and low-molecular-weight DNICs in vitro has been characterized with a characteristic EPR signal at g = 2.03. In addition, complex 2' treated human erythroleukemia K562 cancer cells exposed to UV-A light greatly decreased the percentage survival of the cell cultures. (c) 2006 Elsevier B.V. All rights reserved.