Multivalent Complex Salts of Copper: Synthesis and X‐Ray Structural Analysis of [CuII(en)3][CuI4{(NNNPh)2C6H4}3] (en = ethylendiamine), an anionic Tris‐1,3‐bis(phenyltriazenide)benzene Complex of Tetrakis‐Copper(I)

An ethanolic solution of CuCl / ethylendiamine reacts with 1.3‐bis‐ (phenyltriazene)benzene in THF leading to the deprotonation of the bis triazene ligand to give orange crystals of Cu^II(en)₃]Cu^I₄{(NNN‐Ph)₂C₆H₄}₃], an example of a rare complex salt of copper with mixed valence states. In the anion complex Cu^I₄{(NNNPh)₂C₆H₄}₃]^2? the copper(I) ions are disposed linearly as single, bridged pairs in the two extremes of an axis, each of them presenting a trigonal bipyramidal alike coordination arrangement.