金属有机框架UiO-66中的[铁铁]氢化酶活性位点模型化学
[FeFe] Hydrogenase active site model chemistry in a UiO-66 metal-organic framework.
作者信息
Pullen Sonja, Roy Souvik, Ott Sascha
机构信息
Department of Chemistry, Ångström Laboratory, Uppsala University, Box 523, 75120, Uppsala, Sweden.
出版信息
Chem Commun (Camb). 2017 May 4;53(37):5227-5230. doi: 10.1039/c7cc01620d.
Abstract
The reactivity of [Fe(dcbdt)(CO)] (1) confined in a UiO-66(Zr) metal-organic framework towards CO ligand substitutions with phosphines of different sizes was investigated. The reaction with smaller phosphines (PX, X = Me, Et) is more selective compared to analogous reactions in homogenous solution phase, and two CO ligands at up to 80% of all [FeFe] sites in UiO-66-1 are replaced. The produced [Fe(dcbdt)(CO)(PX)] complexes in the UiO-66 matrix behave like typical [FeFe] hydrogenase active site model complexes, are reduced at more cathodic potentials than their hexacarbonyl analogues, and form bridging hydrides under acidic conditions.
摘要
研究了限制在UiO-66(Zr)金属有机框架中的[Fe(dcbdt)(CO)] (1) 与不同大小膦类进行CO配体取代反应的活性。与均相溶液相中的类似反应相比，与较小膦类（PX，X = Me，Et）的反应更具选择性，并且UiO-66-1中高达80%的所有[FeFe]位点上的两个CO配体被取代。在UiO-66基质中生成的[Fe(dcbdt)(CO)(PX)]配合物表现得像典型的[FeFe]氢化酶活性位点模型配合物，在比其六羰基类似物更负的电位下被还原，并在酸性条件下形成桥连氢化物。
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