Catalytic reduction of N2 to NH3 by an Fe-N2 complex featuring a C-atom anchor.
Catalytic reduction of N2 to NH3 by an Fe-N2 complex featuring a C-atom anchor.
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DOI：
10.1021/ja4114962
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发表时间：
2014-01-22
影响因子：
15
通讯作者：
Peters JC
中科院分区：
文献类型：
--
作者：
Creutz SE;Peters JC
虽然最近的光谱研究已经确定在fe -氮酶的铁钼辅助因子（FeMoco）中心存在间隙碳原子，但其作用尚不清楚。我们研究了Fe- n2模型化学，以探索一种假设，即这个c原子（以前表示为轻x原子）可能与Fe中心提供灵活的反式相互作用，从而暴露出Fe- n2结合位点。在这种情况下，我们现在报道了一种具有轴向碳供体的新型三（磷酸）烷基（CPiPr3）配体的铁配合物。我们已经确定，这个支架中的铁中心以三种不同的结构特征氧化态将二氮反式与钙基原子锚结合。在还原过程中观察到铁-钙基延长，反映了铁-钙基相互作用中显著的离子特性。阴离子（CPiPr3）FeN2-可以被硅基亲电试剂功能化生成（CPiPr3）Fe-N2SiR3。（CPiPr3）FeN2-在-78℃、1atm N2（4.6当量NH3/Fe）条件下提供电子和质子时，也可作为N2还原为NH3的适度催化剂。
While recent spectroscopic studies have established the presence of an interstitial carbon atom at the center of the iron-molybdenum cofactor (FeMoco) of MoFe-nitrogenase, its role is unknown. We have pursued Fe-N2 model chemistry to explore a hypothesis whereby this C-atom (previously denoted as a light X-atom) may provide a flexible trans interaction with an Fe center to expose an Fe-N2 binding site. In this context, we now report on Fe complexes of a new tris(phosphino)alkyl (CPiPr3) ligand featuring an axial carbon donor. It is established that the iron center in this scaffold binds dinitrogen trans to the Calkyl-atom anchor in three distinct and structurally characterized oxidation states. Fe-Calkyl lengthening is observed upon reduction, reflective of significant ionic character in the Fe-Calkyl interaction. The anionic (CPiPr3)FeN2- species can be functionalized by a silyl electrophile to generate (CPiPr3)Fe-N2SiR3. (CPiPr3)FeN2- also functions as a modest catalyst for the reduction of N2 to NH3 when supplied with electrons and protons at -78 °C under 1 atm N2 (4.6 equiv NH3/Fe).
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影响因子：
4.6
作者：
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通讯作者：
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影响因子：
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影响因子：
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作者：
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