Interaction of nitric oxide with tetrathiolato iron(II) complexes: Relevance to the reaction pathways of iron nitrosyls in sulfur-rich biological coordination environments
Interaction of nitric oxide with tetrathiolato iron(II) complexes: Relevance to the reaction pathways of iron nitrosyls in sulfur-rich biological coordination environments
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DOI：
10.1021/ja060186n
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发表时间：
2006-03-22
影响因子：
15
通讯作者：
Lippard, SJ
中科院分区：
文献类型：
--
作者：
Harrop, TC;Song, DT;Lippard, SJ
在铁硫蛋白位点由半胱氨酸残基配位形成二亚硝酰铁络合物（DNIC）的机制在化学文献中很少受到关注。作为阐明这一机制和表征新的铁-亚硝酰基中间体的合乎逻辑的第一步，我们研究了NO（g）和NO+与铁-硫复合物的相互作用，这些复合物被选择来模拟生物学中富硫的铁位点。NO（g）与[Fe（StBu）4]2-的反应干净地得到单亚硝酰基络合物[Fe（StBu）3（NO）]-（1），这是在该化学中引起的先前未知的物种。[Fe（StBu）4]2-与NO衍生物如NO+反应，生成相应的二亚硝酰基S-桥连的胭脂红酯[Fe 2（μ-StBu）2（NO）4]（2）。亚硝酰配合物1和2可化学转化为DNIC [Fe（StBu）2（NO）2]-（3）。结果应有助于在光谱鉴定和阐明的反应途径的亚硝基化铁在生物相关的富硫协调环境。
The mechanism of formation of dinitrosyl iron complexes (DNICs) coordinated by cysteine residues at iron−sulfur protein sites has received little attention in the chemical literature. As a logical first step toward elucidating this mechanism and characterizing new iron−nitrosyl intermediates, we investigated the interaction of NO (g) and NO+with iron−sulfur complexes chosen to mimic sulfur-rich iron sites in biology. The reaction of NO (g) with [Fe(StBu)4]2-cleanly affords the mononitrosyl complex, [Fe(StBu)3(NO)]-(1), a previously unknown species evoked in this chemistry. Reaction of [Fe(StBu)4]2-with NO derivatives, such as NO+, yields the corresponding dinitrosyl S-bridged Roussin red ester [Fe2(μ-StBu)2(NO)4] (2). The nitrosyl complexes1and2can chemically convert to the DNIC, [Fe(StBu)2(NO)2]-(3). The results should aid in the spectroscopic identification and elucidation of reaction pathways for the nitrosylation of iron in biologically related sulfur-rich coordination environments.