Details

Autor(en) / Beteiligte

• Semenov, Artem V
• Baykov, Sergey V
• Soldatova, Natalia S
• Geyl, Kirill K
• Ivanov, Daniil M
• Frontera, Antonio
• Boyarskiy, Vadim P
• Postnikov, Pavel S
• Kukushkin, Vadim Yu

Titel

Noncovalent Chelation by Halogen Bonding in the Design of Metal-Containing Arrays: Assembly of Double σ-Hole Donating Halolium with Cu I -Containing O,O-Donors

Ist Teil von

• Inorganic chemistry, 2023-04, Vol.62 (15), p.6128-6137

Ort / Verlag

United States

Erscheinungsjahr

2023

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• Five new copper(I) complexes─composed of the paired dibenzohalolium and [CuL ] (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) ](BF ), sodium 1,2,4-oxadiazolates, and dibenzohalolium triflates (or trifluoroacetates). This reaction is different from the previously reported Cu -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 -CH ···π interactions, which were also quantified.