A Triad of Highly Reduced, Linear Iron Nitrosyl Complexes: {FeNO}(8-10).
A Triad of Highly Reduced, Linear Iron Nitrosyl Complexes: {FeNO}(8-10).
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高度还原的线性硝基基络合物的三合会：{feno}（8-10）。
DOI：
10.1002/anie.201605403
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发表时间：
2016-09-19
影响因子：
16.6
通讯作者：
Peters, Jonas C.
中科院分区：
文献类型：
--
作者：
Chalkley, Matthew J.;Peters, Jonas C.
鉴于Fe-NO络合物在人类生物学和全球氮循环中的重要性，人们一直有兴趣了解它们的不同电子结构。在这里，我们描述了一系列有趣的氧化还原系列的可分离的亚硝基铁络合物，这些络合物是由三膦基硼(TPB)配体稳定的。这些结构表征的亚硝基铁络合物存在于以下高度降低的Enemark-Feltham数中：{FeNO}8，{FeNO}9，和{FeNO}10。这些{FeNO}8-10化合物都是低自旋的，并且具有线性但强烈激活的一氧化氮配体。使用穆斯堡尔、EPR、核磁共振、UV/VIS和IR光谱，结合密度泛函计算，提供了对这一不常见的氧化还原亚硝酸铁系列的电子结构的洞察。特别是，这些数据共同表明，{TPBFeNO}8-10都是显著共价的。这种共价性可能是这个体系在三个高度还原的氧化还原状态下保持稳定的原因，这三个状态与异常高的Enemark-Feltham数相关。模型铁-亚硝基络合物由于其生物学意义和迷人的潜在电子结构而被广泛研究。然而，具有高Enemark-Feltham数(8-10)的物种仍然很少。在这里，我们报道了一个不寻常的氧化还原系列的{FeNO}8-10络合物由一个三膦基硼烷支撑。这些物种在整个系列中保持一个线性的Fe-N-O角；已经用光谱学研究了这种非典型行为的潜在原因。
Given the importance of Fe–NO complexes in both human biology and the global nitrogen cycle, there has been interest in understanding their diverse electronic structures. Herein we describe an interesting redox series of isolable iron nitrosyl complexes stabilized by a tris(phosphine)borane (TPB) ligand. These structurally characterized iron nitrosyl complexes reside in the following highly reduced Enemark-Feltham numbers: {FeNO}8, {FeNO}9, and {FeNO}10. These {FeNO}8–10 compounds are each low-spin, and feature linear yet strongly activated nitric oxide ligands. Use of Mössbauer, EPR, NMR, UV/Vis, and IR spectroscopies, in conjunction with DFT calculations, provide insight into the electronic structures of this uncommon redox series of iron nitrosyls. In particular, the data collectively suggest that {TPBFeNO}8–10 are all remarkably covalent. This covalency is likely responsible for the stability of this system across three highly reduced redox states that correlate with unusually high Enemark-Feltham numbers. Model iron-nitrosyl complexes have been well-studied due to their biological significance and fascinating underlying electronic structures. However, species with high Enemark-Feltham numbers (8–10) remain rare. Herein we report an unusual redox series of {FeNO}8–10 complexes supported by a tris(phosphine)borane. These species maintain a linear Fe–N–O angle throughout the series; the underlying reasons for this atypical behavior have been investigated spectroscopically.
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影响因子：
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影响因子：
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作者：
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通讯作者：
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影响因子：
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作者：
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通讯作者：
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