Silyl Transfer Pathway to a Ce(IV) Imido Complex
Silyl Transfer Pathway to a Ce(IV) Imido Complex
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DOI：
10.1021/acs.organomet.8b00366
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发表时间：
2018-12-10
期刊：
影响因子：
2.8
通讯作者：
Schelter, Eric J.
中科院分区：
文献类型：
--
作者：
Cheisson, Thibault;Solola, Lukman A.;Schelter, Eric J.
镧系元素阳离子和阴离子p区元素片段之间的多重键的形成和稳定是具有挑战性的，并且迄今为止仅报道了这种末端络合物的几个实例。值得注意的是，所有报道的镧系元素-亚氨基部分的合成路线都采用去质子化作为关键形成步骤。在本报告中，我们描述了生成的Ce（IV）亚胺络合物的三甲基甲硅烷基基团转移途径。实验和计算证据支持双分子亲核取代机制的平衡过程。
The formation and stabilization of multiple bonds between a lanthanide cation and an anionic p-block element fragment are challenging, and only a few examples of such terminal complexes have been reported to date. Notably, all reported synthetic routes to lanthanide-imido moieties employed deprotonation as the key formation step. In the present report, we describe the generation of a Ce(IV) imido complex by a trimethylsilyl group transfer pathway. Experimental and computational evidence supports an equilibrium proceeding by a bimolecular nucleophilic substitution mechanism.