Reactions of low valent transition metal complexes with fluorocarbons. Part XXIII. Pentafluorophenyl azide and hexafluoroazomethane
作者:J. Ashley-Smith、M. Green、F. G. A. Stone
DOI:10.1039/dt9720001805
日期:——
Reaction between pentafluorophenylazide and Ni(1,5-C8H12)2 affords green crystals of a tetra-azadiene complex Ni[(C6F5)2N4](1,5-C8H12). Cyclo-octa-1,5-diene is displaced by the ligands L = PPh3, PPh2Me, PPhMe2, or P(OMe)3 and L2= bipyridyl to form Ni[(C6F5)2N4]L2. 1H N.m.r. measurements on the bisdimethylphenylphosphine and bis(trimethyl phosphite) Complexes suggest two different modes of bonding
五氟苯基叠氮化物与Ni(1,5-C 8 H 12)2之间的反应产生四氮杂二烯配合物Ni [(C 6 F 5)2 N 4 ](1,5-C 8 H 12)的绿色晶体。环辛基-1,5-二烯被配体L = PPh 3,PPh 2 Me,PPhMe 2或P(OMe)3和L 2 =联吡啶取代,形成Ni [(C 6 F 5)2 N 4 ] L 2。1个对双二甲基苯基膦和双(亚磷酸三甲酯)配合物的H Nmr测量表明,四氮杂二烯配体的键合方式有两种。
Reversible C−C Bond Cleavage of a Cobalt Diketimide into an Elusive Cobalt Aryl Nitrenoid Complex
作者:Yunjung Baek、Theodore A. Betley
DOI:10.1002/anie.202115437
日期:2022.4.19
A CoII diketimide complex was synthesized via an oxidative group transfer reaction of an aryl azide with a CoI synthon supported by a sterically demanding (TrL) dipyrrin ligand. Kinetic analysis established a pre-equilibrium between the diketimide and its monomeric Co aryl nitrenoid complex that is competent for intermolecular H-atom abstraction.
Co II双酮酰亚胺络合物是通过芳基叠氮化物与 Co I合成子的氧化基团转移反应合成的,Co I 合成子由空间要求高的 ( Tr L) 双吡啶配体支持。动力学分析在双酮酰亚胺与其单体 Co 芳基亚硝基络合物之间建立了预平衡,该络合物能够进行分子间 H 原子提取。