Cyclopentadienyl-Like Ligand as a Reactive Site in Half-Sandwich Bis(amidinato) Rare-Earth-Metal Complexes: An Efficient Application in Catalytic Addition of Amines to Carbodiimides
Cyclopentadienyl-Like Ligand as a Reactive Site in Half-Sandwich Bis(amidinato) Rare-Earth-Metal Complexes: An Efficient Application in Catalytic Addition of Amines to Carbodiimides
复制标题
环戊二烯基类配体作为半夹心双(脒基)稀土金属配合物中的反应位点：在胺催化加成到碳二亚胺中的有效应用
DOI：
10.1021/om5002793
复制
发表时间：
2014
期刊：
影响因子：
2.8
通讯作者：
Xi Zhenfeng
中科院分区：
文献类型：
--
作者：
Wei Peng-Hui;Xu Ling;Song Li-Cheng;Zhang Wen-Xiong;Xi Zhenfeng
以Cp′Ln（CH 2SiMe 3）2（THF）（Ln = Y，Dy，Er，Lu）和脒为原料，通过1：2的酸碱反应合成了一系列Cp′/双脒基（Cp′ = η5-C5 Me 4（SiMe 3））混合稀土配合物。这些Cp′/双脒基配合物对胺与N-二甲酰亚胺的加成反应显示出良好的催化活性。双核氨基镥配合物的分离、结构表征和催化应用表明，催化循环是由Cp′的解离引发的。这些结果表明Cp′首次作为反应中心产生了活性Ln-N物种。
A series of mixed Cp′/bis(amidinato) (Cp′ = η5-C5Me4(SiMe3)) lanthanide complexes were synthesized by the 1:2 acid–base reaction between Cp′Ln(CH2SiMe3)2(THF) (Ln = Y, Dy, Er, Lu) and amidines. These Cp′/bis(amidinato) complexes showed excellent catalytic activity for the addition of amines to carbodiimides, yielding the corresponding guanidines. Isolation, structural characterization, and catalytic application of the binuclear lutetium amido complex showed clearly that the catalytic cycle was initiated by the dissociation of Cp′. These results demonstrated that Cp′, for the first time, acted as a reactive site to yield the active Ln–N species.