Related Experiment Video
Updated: Aug 4, 2025

Synthesis of a Water-soluble Metal–Organic Complex Array
Published on: October 8, 2016
Noncovalent Chelation by Halogen Bonding in the Design of Metal-Containing Arrays: Assembly of Double σ-Hole Donating
Artem V Semenov1, Sergey V Baykov1,2, Natalia S Soldatova2
1Institute of Chemistry, Saint Petersburg State University, 7/9 Universitetskaya Nab., Saint Petersburg 199034, Russian Federation.
Abstract:
Five new copper(I) complexes─composed of the paired dibenzohalolium and [CuL2]- (L = 1,2,4-oxadiazolate) counterions in which O,O-atoms of the anion are simultaneously linked to the halogen atom─were generated and isolated as the solid via the three-component reaction between [Cu(MeCN)4](BF4), sodium 1,2,4-oxadiazolates, and dibenzohalolium triflates (or trifluoroacetates). This reaction is different from the previously reported CuI-catalyzed arylation of 1,2,4-oxadiazolones by diaryliodonium salts. Inspection of the solid-state X-ray structures of the complexes revealed the strong three-center X···O,O (X = Br, I) halogen bonding occurred between the oxadiazolate moieties and dibenzohalolium cation. According to performed theoretical calculations, this noncovalent interaction (or noncovalent chelation) was recognized as the main force in the stabilization of the copper(I) complexes. An explanation for the different behavior of complexes, which provide either chelate or nonchelate binding, is based on the occurrence of additional -CH3···π interactions, which were also quantified.
Related Concept Videos
Metal-Ligand Bonds
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
Complexation Equilibria: The Chelate Effect
Valence Bond Theory
Complexation Equilibria: Factors Influencing Stability of Complexes
Extraction: Advanced Methods
Ionic Bonding and Electron Transfer

