Multimetallic cooperativity in activation of dinitrogen at iron-potassium sites
Multimetallic cooperativity in activation of dinitrogen at iron-potassium sites
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DOI：
10.1039/c3sc52487f
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发表时间：
2014-01-01
期刊：
影响因子：
8.4
通讯作者：
Holland, Patrick L.
中科院分区：
文献类型：
--
作者：
Chiang, Karen P.;Bellows, Sarina M.;Holland, Patrick L.
可溶性铁-氧-钾组装体与N-2的反应提供了对多金属N-2配位机制的深入了解。我们报告了一系列非常富电子的三坐标，β-diketiminate支持的铁（I）酚盐配合物，这是亚稳的，但其特征在于在Ar下的晶体学和溶液方法。单体和二聚体的Fe-OPh-K化合物的特征在于，和它们的铁环境是非常相似的固体和溶液状态。在二聚体中，钾离子将两半的酚氧和芳环结合在一起，形成一个灵活的二铁核。单体和二聚铁（I）化合物与N-2的反应令人惊讶地不同：单核铁（I）络合物不与N-2反应，但二聚Fe 2K 2络合物迅速反应，得到二铁-N-2产物。计算研究表明，二聚体的快速N-2反应的关键是两个铁原子的预组织。因此，Fe（削弱N-N键）和K（使Fe原子定向）之间的合作可以用于为N-2反应创建低能量路径。
The reaction of soluble iron-oxygen-potassium assemblies with N-2 gives insight into the mechanisms of multimetallic N-2 coordination. We report a series of very electron-rich three-coordinate, beta-diketiminate-supported iron(I) phenoxide complexes, which are metastable but have been characterized under Ar by both crystallography and solution methods. Both monomeric and dimeric Fe-OPh-K compounds have been characterized, and their iron environments are very similar in the solid and solution states. In the dimer, potassium ions hold together the phenoxide oxygens and aryl rings of the two halves, to give a flexible diiron core. The reactions of the monomeric and dimeric iron(I) compounds with N-2 are surprisingly different: the mononuclear iron(I) complexes give no reaction with N-2, but the dimeric Fe2K2 complex reacts rapidly to give a diiron-N-2 product. Computational studies show that the key to the rapid N-2 reaction of the dimer is the preorganization of the two iron atoms. Thus, cooperation between Fe (which weakens the N-N bond) and K (which orients the Fe atoms) can be used to create a low-energy pathway for N-2 reactions.