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用于酮转移氢化反应的二钌(II)-NNN钳形配合物催化剂

Diruthenium(ii)-NNN pincer complex catalysts for transfer hydrogenation of ketones.

作者信息

Chai Huining, Wang Qingfu, Liu Tingting, Yu Zhengkun

机构信息

Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023, P. R. China.

出版信息

Dalton Trans. 2016 Nov 28;45(44):17843-17849. doi: 10.1039/c6dt03620a. Epub 2016 Oct 24.

Abstract

Dinuclear ruthenium(ii)-NNN pincer complexes bearing a π linker-supported bis(pyrazolyl-imidazolyl-pyridine) ligand were synthesized and structurally characterized, and they exhibited excellent catalytic activity for the transfer hydrogenation of ketones in refluxing isopropanol, reaching TOF values up to 1.3 × 10 h. Compared with the corresponding mononuclear Ru(ii)-NNN pincer complexes, the bimetallic complexes could be applied at concentrations as low as 0.03 mol% Ru and demonstrated remarkably enhanced catalytic activity in the transfer hydrogenation reactions of ketones. The high catalytic activity of the diruthenium(ii) complexes is attributed to the excellent stability and possible cooperativity of the two coordinated Ru(ii) metal centers through the π linker. The present synthetic methodology has established an applicable strategy to construct highly active bimetallic NNN pincer complex catalysts.

摘要

合成并表征了带有π连接基支撑的双(吡唑基-咪唑基-吡啶)配体的双核钌(II)-NNN钳形配合物,它们在回流异丙醇中对酮的转移氢化表现出优异的催化活性,TOF值高达1.3×10³ h⁻¹。与相应的单核Ru(II)-NNN钳形配合物相比,双金属配合物可在低至0.03 mol% Ru的浓度下应用,并在酮的转移氢化反应中表现出显著增强的催化活性。二钌(II)配合物的高催化活性归因于两个配位的Ru(II)金属中心通过π连接基具有优异的稳定性和可能的协同作用。目前的合成方法建立了一种构建高活性双金属NNN钳形配合物催化剂的适用策略。

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