- 通过(PNNP)Fe配合物实现末端炔烃的选择性二聚化。

-selective dimerization of terminal alkynes by a (PNNP)Fe complex.

作者信息

Stevens Jeremiah E, Miller Justin D, Fitzsimmons Matthew C, Moore Curtis E, Thomas Christine M

机构信息

Department of Chemistry and Biochemistry, The Ohio State University, 100 W. 18th Ave., Columbus, OH 43210, USA.

出版信息

Chem Commun (Camb). 2024 May 9;60(39):5169-5172. doi: 10.1039/d4cc00469h.

DOI:10.1039/d4cc00469h

PMID:38639737

Abstract

A tetradentate bis(amido)bis(phosphine) Fe complex, (PNNP)Fe, is shown to activate the terminal C-H bond of aryl alkynes across its Fe-N bonds. (PNNP)Fe is also shown to catalytically dimerize terminal aryl alkynes to produce 1,3-enynes with : ratios as high as 96 : 4 with yields up to 95% and loadings as low as 1 mol% at 30 °C in 2 h. A plausible metal-ligand cooperative mechanism invoking a vinylidene intermediate is proposed.

摘要

一种四齿双（酰胺）双（膦）铁配合物（PNNP）Fe，被证明能通过其铁氮键活化芳基炔烃的末端碳氢键。（PNNP）Fe还被证明能催化末端芳基炔烃二聚，在30℃下2小时内生成1,3 - 烯炔，其顺反比高达96∶4，产率高达95%，负载量低至1 mol%。提出了一种合理的涉及亚乙烯基中间体的金属 - 配体协同机制。