N-H Activation of Amines and Ammonia by Ru via Metal-Ligand Cooperation
N-H Activation of Amines and Ammonia by Ru via Metal-Ligand Cooperation
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DOI：
10.1021/ja103130u
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发表时间：
2010-06-30
影响因子：
15
通讯作者：
Milstein, David
中科院分区：
文献类型：
--
作者：
Khaskin, Eugene;Iron, Mark A.;Milstein, David
本文报道了Ru(II)氨络合物氨键活化的非氧化加成途径。钳形络合物1通过金属-配体合作裂解N-H键，涉及钳形配体的芳构化，而不改变金属的形式氧化态。富电子的N-H键底物导致可逆的活化，而贫电子的底物产生稳定的活化产物。利用Nd3的同位素标记研究和密度泛函理论计算阐明了N-H的活化机理。
A nonoxidative addition pathway for the activation of NH bonds of ammonia Ru(II) complex is reported. The pincer complex 1 cleaves N-H bonds via metal-ligand cooperation involving aromatization of the pincer ligand without a change in the formal oxidation state of the metal. Electron-rich N-H bond substrates lead to reversible activation, while electron-poor substrates result in stable activation products. Isotopic labeling studies using ND3 as well as density functional theory calculations were used to shed light on the N-H activation mechanism.