一锅法合成高张力金属亚乙烯基和金属卡宾。
One-Pot Synthesis of High-Strained Metal Vinylidene and Metal Carbyne.
作者信息
Huang Fanping, Yan Zhewei, Zheng Xuejuan, Cai Yapeng, Zhang Hong, Xia Haiping
机构信息
State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.
Shenzhen Grubbs Institute, Department of Chemistry, Southern University of Science and Technology, Shenzhen, 518055, China.
出版信息
Chemistry. 2022 Sep 27;28(54):e202201229. doi: 10.1002/chem.202201229. Epub 2022 Aug 10.
A novel one-pot reaction producing a metal vinylidene structure in a five-membered ring by cyclization of a multiyne has been achieved. The ring strain and the high stability of the cyclic metal vinylidene complexes have been analyzed experimentally and computationally. The metal vinylidene unit in a fused-ring complex is unreactive to both nucleophiles and electrophiles. It reacts however at the nearby carbonyl group achieving the unprecedented conversion of metal tributing factors for the aromaticity-driven process has been studied by DFT calculations.
通过多炔的环化反应，实现了一种在五元环中生成金属亚乙烯基结构的新型一锅法反应。已通过实验和计算分析了环状金属亚乙烯基配合物的环张力和高稳定性。稠环配合物中的金属亚乙烯基单元对亲核试剂和亲电试剂均无反应活性。然而，它会在附近的羰基处发生反应，实现了前所未有的转化。通过密度泛函理论（DFT）计算研究了芳香性驱动过程中金属配体因素。
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