Structural transformation and catalytic hydrogenation activity of amidinate-protected copper hydride clusters.
Structural transformation and catalytic hydrogenation activity of amidinate-protected copper hydride clusters.
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DOI：
10.1038/s41467-022-29819-y
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发表时间：
2022-04-19
影响因子：
16.6
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中科院分区：
文献类型：
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氢化铜是重要的加氢催化剂，但其稳定性差阻碍了实际应用。配体工程是解决这一问题的有效策略。具有四个 N-供体的脒配体 N,N'-二（5-三氟甲基-2-吡啶基）甲脒（Tf-dpf）已被用作合成稳定的氢化铜簇的保护剂：具有三个界面 μ5-H 和 Cu11H3(Tf-dpf)6(OAc)2 (Cu11) [Cu12H3(Tf-dpf)6(OAc)2]·OAc (Cu12) 具有三个间隙μ6-H。由于 Tf-dpf 的灵活性，我们观察到了 Cu11 和 Cu12 之间溶剂触发的可逆相互转化。 Cu11 在 4-硝基苯酚还原成 4-氨基苯酚方面显示出高活性，而 Cu12 显示出非常低的活性。氘化实验证明氢化物的类型是决定催化活性的关键，因为Cu11中的界面μ5-H物种参与催化循环，而Cu12中的间隙μ6-H物种则不参与。这项工作强调了氢化物在催化氢化活性方面的作用。氢化铜因其令人兴奋的结构化学及其在加氢催化中的应用而受到研究。在这里，作者揭示了脒基配体在产生两个密切相关的氢化铜簇（催化氢化活性截然不同）中的作用。
Copper hydrides are important hydrogenation catalysts, but their poor stability hinders the practical applications. Ligand engineering is an effective strategy to tackle this issue. An amidinate ligand, N,N′-Di(5-trifluoromethyl-2-pyridyl)formamidinate (Tf-dpf) with four N-donors has been applied as a protecting agent in the synthesis of stable copper hydride clusters: Cu11H3(Tf-dpf)6(OAc)2 (Cu11) with three interfacial μ5-H and [Cu12H3(Tf-dpf)6(OAc)2]·OAc (Cu12) with three interstitial μ6-H. A solvent-triggered reversible interconversion between Cu11 and Cu12 has been observed thanks to the flexibility of Tf-dpf. Cu11 shows high activity in the reduction of 4-nitrophenol to 4-aminophenol, while Cu12 displays very low activity. Deuteration experiments prove that the type of hydride is the key in dictating the catalytic activity, for the interfacial μ5-H species in Cu11 are involved in the catalytic cycle whereas the interstitial μ6-H species in Cu12 are not. This work highlights the role of hydrides with regard to catalytic hydrogenation activity. Copper hydrides have been studied for their exciting structural chemistry and applications in hydrogenation catalysis. Here, the authors uncover the role of the amidinate ligand in yielding two closely related copper hydride clusters with quite different catalytic hydrogenation activity.
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