Muonium Chemistry at Diiron Subsite Analogues of [FeFe]-Hydrogenase.
Muonium Chemistry at Diiron Subsite Analogues of [FeFe]-Hydrogenase.
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DOI：
10.1002/anie.201607109
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发表时间：
2016-11-14
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影响因子：
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通讯作者：
Jayasooriya UA
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文献类型：
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作者：
Wright JA;Peck JN;Cottrell SP;Jablonskytė A;Oganesyan VS;Pickett CJ;Jayasooriya UA
金属氧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/或电子化形成这些位点对于充分利用这些系统的潜力具有重要价值。在这里，我们表明，μ 鎓自由基（μ.），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.会发生和H一样的化学反应并且由于其短的寿命（微秒）和独特的击穿特征而可以被直接观察到。通过植入穆。三个模型的[FeFe]-氢化酶活性位点，我们已经能够检测到直接相关的氢化物化学这些系统的关键muoniated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.