零价镍催化的芳炔配合物异构化反应：通过碳氢键而非碳氟键活化形成双核一价镍配合物。

Nickel(0)-catalyzed isomerization of an aryne complex: formation of a dinuclear Ni(I) complex via C-H rather than C-F bond activation.

作者信息

Keen Alana L, Johnson Samuel A

机构信息

Department of Chemistry & Biochemistry, University of Windsor, Windsor, Ontario, Canada N9B 3P4.

出版信息

J Am Chem Soc. 2006 Feb 15;128(6):1806-7. doi: 10.1021/ja0572553.

DOI:10.1021/ja0572553

PMID:16464076

Abstract

The reaction of the aryne complex (PEt3)2Ni(eta2-C6H2-4,5-F2) with a catalytic amount of Ni(PEt3)2 results in a dinuclear Ni(I) complex from the coupling of the isomer (PEt3)2Ni(eta2-C6H2-3,4-F2), obtained via rearrangement of the aromatic C-H bonds, which demonstrates that Ni(PEt3)2 is kinetically capable of C-H bond activation, even in the presence of C-F bonds. The intermediate [(PEt3)2Ni]2(mu-eta2:eta2-C6H2-4,5-F2) was isolated and crystallographically characterized; the mu-eta2:eta2-bonding mode observed is unprecedented in aryne chemistry.

摘要

芳烃配合物(PEt3)2Ni(η2-C6H2-4,5-F2)与催化量的Ni(PEt3)2反应，通过芳族C-H键重排得到的异构体(PEt3)2Ni(η2-C6H2-3,4-F2)偶联生成双核Ni(I)配合物，这表明即使存在C-F键，Ni(PEt3)2在动力学上也能够实现C-H键活化。中间体[(PEt3)2Ni]2(μ-η2:η2-C6H2-4,5-F2)已被分离并通过晶体学进行了表征；所观察到的μ-η2:η2键合模式在芳烃化学中是前所未有的。