Generating high-valent iron with light: photochemical dynamics from femtoseconds to seconds
Generating high-valent iron with light: photochemical dynamics from femtoseconds to seconds
复制标题
用光产生高价铁：从飞秒到秒的光化学动力学
DOI：
10.1080/0144235x.2014.973197
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发表时间：
2014
影响因子：
6.1
通讯作者：
P. Vöhringer
中科院分区：
文献类型：
--
作者：
Joel Torres;P. Vöhringer
铁最丰富的氧化态是亚铁态和铁态，分别是+II和+III。高价铁化合物含有铁中心在特殊氧化态，+IV， +V和+VI。这些物种对于催化许多生物化学或技术相关的分子转化至关重要。由于其不寻常的电子结构，高价铁化合物通常具有极强的活性，因此在其催化作用过程中难以检测到。因此，目前世界范围内正在进行一项协调一致的研究工作，以合成和分析低分子量模型系统，目的是更好地了解高价铁配合物的反应性，并长期开发它们作为需要惰性键激活的重要化学转化的催化剂。特别活跃的是高价铁，其末端有一个铁-氮键，被称为氮化铁化合物，其中的金属像血红蛋白一样以四倍对称的配位几何形状嵌入。迄今为止，它们的分离尚未完成，但很少有非血红素模型系统通过光化学方法制备并在低温固体基质中低温捕获。最近，复杂的时间分辨红外（IR）光谱已经成功地在液体溶液和室温下，即在生物化学和技术相关条件下，暂时捕获这种难以捉摸的伪八面体氮铁，甚至允许对其反应性进行初步研究。这篇综述将总结我们目前对通过这些强大的时间分辨红外光谱所看到的光化学途径中涉及的这种高价铁物种的分子水平机制的理解状态。
The most abundant oxidation states of iron are the ferrous and ferric states, +II and +III, respectively. High-valent iron compounds contain Fe centres at the extraordinary oxidation states, +IV, +V and +VI. Such species are of paramount importance for the catalysis of a number of biochemically or technologically relevant molecular transformations. Because of their unusual electronic structure, high-valent iron compounds are generally extremely reactive and hence, difficult to detect during their catalytic action. Therefore, a concerted research effort is currently undertaken worldwide to synthesise and analyse low molecular-weight model systems with the goal to better understand the reactivities of high-valent Fe-complexes and the long-term vision to exploit them as catalysts in important chemical transformations requiring inert bond activation. Particularly reactive are high-valent iron species that feature a terminal iron–nitrogen bond, so called nitridoiron compounds, and in which the metal is embedded in a fourfold-symmetrical coordination geometry like in haem proteins. Their isolation has not been accomplished to date, but very few non-haem model systems have been prepared by photochemical means and cryo-trapped in low-temperature solid matrices. Very recently, sophisticated time-resolved infrared (IR) spectroscopies have been successful at temporally trapping such elusive pseudo-octahedral nitridoiron species even in liquid solution and at room temperature, i.e. under biochemically and technologically relevant conditions, and to even allow for a preliminary study of their reactivity. This review will summarise our current state of understanding of the molecular-level mechanisms that are involved in the photochemical route to such high-valent iron species as seen through these powerful time-resolved IR spectroscopies.
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影响因子：
4.6
作者：
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通讯作者：
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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：
20.6
作者：
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通讯作者：
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