Overview and new insights into the thiol reactivity of coordinated NO in {MNO}(6/7/8) (M = Fe, Co) complexes.
Overview and new insights into the thiol reactivity of coordinated NO in {MNO}(6/7/8) (M = Fe, Co) complexes.
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对 {MNO}(6/7/8) (M = Fe, Co) 配合物中配位 NO 的硫醇反应性的概述和新见解。
DOI：
10.1021/acs.inorgchem.5b00883
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发表时间：
2015
影响因子：
4.6
通讯作者：
Harrop,ToddC
中科院分区：
文献类型：
--
作者：
Rhine,MelodyA;Sanders,BrianC;Patra,AshisK;Harrop,ToddC
游离NO（NO+、NO·和NO-）与硫醇（RSH）的反应性相对较好地理解，并且NO部分的氧化态通常决定反应的结果。然而，NO/RSH相互作用通常在金属中心介导，并且当与第一行过渡金属（例如，Fe，Co）值得进一步研究。一些金属结合的NO部分（特别是NO+，yieldingS-nitrosothiols）已被更彻底地研究，但这些物种的命运仍然高度依赖于条件，对于M-NO-，一个未探索的领域。在此，我们提出了一个概述的硫醇反应与金属亚硝基，导致N-O键活化，配体取代{MNO}片段，和/或氧化还原化学。我们还介绍了我们的结果有关的非血红素{FeNO}7/8配合物[Fe（LN 4pr）（NO）]−/0（1和2）和非咕啉{CoNO} 8配合物[Co（LN 4pr）（NO）]（3），{FeNO} 8配合物的等电子类似物1的硫醇反应性。在其他产物中，1与p-ClPhSH反应得到[Fe 2（μ-SPh-p-Cl）2（NO）4]−（6的阴离子），一种还原的胭脂红酯（rRRE），通过傅立叶变换红外光谱（FTIR）、紫外-可见光谱（UV-vis）、电子顺磁共振（EPR）和X射线衍射进行表征。类似地，1与谷胱甘肽在缓冲液中反应得到相应的rRRE，其也已通过EPR和UV-vis光谱表征。金属和亚硝基的氧化态都有助于这些相互作用的复杂性，因此，我们相应地讨论了不同的产品分布。这些研究揭示了可能通过MNO/RSH相互作用形成的导致NOx活化和{MNO}氧化还原的产物。
The reactivity of free NO (NO+, NO•, and NO–) with thiols (RSH) is relatively well understood, and the oxidation state of the NO moiety generally determines the outcome of the reaction. However, NO/RSH interactions are often mediated at metal centers, and the fate of these species when bound to a first-row transition metal (e.g., Fe, Co) deserves further investigation. Some metal-bound NO moieties (particularly NO+, yieldingS-nitrosothiols) have been more thoroughly studied, yet the fate of these species remains highly condition-dependent and, for M–NO–, an unexplored field. Herein, we present an overview of thiol reactions with metal nitrosyls that result in N–O bond activation, ligand substitution on {MNO} fragments, and/or redox chemistry. We also present our results pertaining to the thiol reactivity of nonheme {FeNO}7/8complexes [Fe(LN4pr)(NO)]−/0(1and2) and the noncorrin {CoNO}8complex [Co(LN4pr)(NO)] (3), an isoelectronic analogue of the {FeNO}8complex1. Among other products, the reaction of1withp-ClPhSH affords [Fe2(μ-SPh-p-Cl)2(NO)4]−(anion of6), a reduced Roussin’s red ester (rRRE), which was characterized by Fourier transform infrared (FTIR), UV–vis, electron paramagnetic resonance (EPR), and X-ray diffraction. Similarly, the reaction of1with glutathione in buffer affords the corresponding rRRE, which has also been spectroscopically characterized by EPR and UV–vis. The oxidation states of the metals and nitrosyls both contribute to the complex nature of these interactions, and as such, we discuss the varying product distribution accordingly. These studies shed insight into the products that may form through MNO/RSH interactions that lead to NOxactivation and {MNO} redox.