Muonium Chemistry at Diiron Subsite Analogues of [FeFe]-Hydrogenase
Muonium Chemistry at Diiron Subsite Analogues of [FeFe]-Hydrogenase
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[FeFe]-氢化酶的二铁亚位类似物的锷化学
DOI：
10.1002/ange.201607109
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发表时间：
2016
影响因子：
--
通讯作者：
Wright J
中科院分区：
文献类型：
--
作者：
Wright J
金属氢化物的化学性质涉及金属中心的一系列催化过程。因此，深入了解通过质子化和/或电子化形成此类位点对于充分开发此类系统的潜力具有重要价值。在这里，我们表明，μ自由基（Mu.）用作氢的低同位素质量类似物，可用于探测金属中心氢化物形成的早期阶段。 Mu. 经历与 H. 相同的化学反应，并且由于其寿命短（以微秒为单位）和独特的击穿特征，可以直接观察到。通过将 Mu 植入 [FeFe]-氢化酶活性位点的三个模型中，我们已经能够检测到与这些系统的氢化物化学直接相关的关键缪化中间体。
The chemistry of metal hydrides is implicated in a range of catalytic processes at metal centers. Gaining insight into the formation of such sites by protonation and/or electronation is therefore of significant value in fully exploiting the potential of such systems. Here, we show that the muonium radical (Mu.), used as a low isotopic mass analogue of hydrogen, can be exploited to probe the early stages of hydride formation at metal centers. Mu.undergoes the same chemical reactions as H.and can be directly observed due to its short lifetime (in the microseconds) and unique breakdown signature. By implanting Mu.into three models of the [FeFe]‐hydrogenase active site we have been able to detect key muoniated intermediates of direct relevance to the hydride chemistry of these systems.