Formation of Zirconocenes Containing Vinyl-imine and Keteniminate Species from Zirconacycles and Diphenylacetonitrile

Formation of Zirconocenes Containing Vinyl-imine and Keteniminate Species from Zirconacycles and Diphenylacetonitrile
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由二氧化锆和二苯乙腈形成含有乙烯基亚胺和烯酮亚胺物种的二茂锆

DOI:
10.1021/om200404p
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发表时间:
2011-06
期刊:
影响因子:
2.8
通讯作者:
Xi, Zhenfeng
Xi, Zhenfeng
中科院分区:
化学2区
文献类型:
--
作者:
Zhao, Jing;Zhang, Shaoguang;Zhang, Wen-Xiong;Xi, Zhenfeng

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第一个定义明确的茂锆配合物处理乙烯基亚胺和keteniminate物种已实现从zirconacyclopentenes或zirconacyclopyrenes和2当量的Ph 2CHCN。首次在一个体系中观察到Ph_2CHCN的多功能效应。该过程通过氮杂环戊二烯中间体及其分子内质子转移进行。此外,在适当的条件下,首次观察到四烷基取代的锆环戊二烯的β,β '-C-C键断裂。
The first well-defined zirconocene complexes processing vinyl-imine and keteniminate species have been achieved from zirconacyclopentenes or zirconacyclopentadienes and 2 equiv of Ph2CHCN. Multifunctional effect of Ph2CHCN is observed for the first time in one system. This process proceeds via the azazirconacyclopentadiene intermediate and its intramolecular proton transfer. Moreover, β,β′-C–C bond cleavage of tetra-alkyl-substituted zirconacyclopentadienes is observed for the first time under the appropriate conditions.
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