A1 Journal article (refereed)
Activation of the Cyano Group at Imidazole via Copper Stimulated Alcoholysis (2019)

Gayfullina, R., Jääskeläinen, S., Koshevoy, I. O., & Hirva, P. (2019). Activation of the Cyano Group at Imidazole via Copper Stimulated Alcoholysis. Inorganics, 7(7), Article 87. https://doi.org/10.3390/inorganics7070087

JYU authors or editors

Publication details

All authors or editors: Gayfullina, Rezeda; Jääskeläinen, Sirpa; Koshevoy, Igor O.; Hirva, Pipsa

Journal or series: Inorganics

eISSN: 2304-6740

Publication year: 2019

Volume: 7

Issue number: 7

Article number: 87

Publisher: MDPI AG

Publication country: Switzerland

Publication language: English

DOI: https://doi.org/10.3390/inorganics7070087

Publication open access: Openly available

Publication channel open access: Open Access channel

Publication is parallel published (JYX): https://jyx.jyu.fi/handle/123456789/65767

Abstract

Reactions of 4,5-dicyano-1-methylimidazole with CuX2 (X = Cl, Br) in alcohol solvents (ethanol and methanol) resulted in the formation of Cu(II) carboximidate complexes [CuCl2(5- cyano-4-C(OEt)N-1-methylimidazole)(EtOH)] (1), [Cu2(µ-Cl)2Cl2(5-cyano-4-C(OMe)N-1-methylimidazole)2] (2), [Cu2(µ-Br)2Br2(5-cyano-4-C(OMe)N-1-methylimidazole)2] (3), and [Cu2(µ-Br)2Br2(5-cyano-4-C(OEt)N-1-methylimidazole)2] (4). The structures were determined by the X-ray crystallographic method, and further spectroscopic and computational methods were employed to explain the structural features. The solvent contributed to the alcoholysis reaction of the cyano group, as the result of which the ligand coordinated to the metal center in bidentate mode forming a five-membered chelating ring. In 1, the solvent also acts as an additional ligand, which coordinates to the metal center of a monomeric complex. In compounds 2–4, two halogen ligands link the metal atoms forming dihalo-bridged copper dimers. The infrared absorption characteristics were verified by simulation of the infrared spectra at the density functional theory level. In addition, the electronic absorption characteristics were explained by simulation of the UV–Vis spectra using the TD-DFT method. Molecular modelling at the DFT level was performed to study the effects of halogen type and steric hindrance of the alkoxy groups in forming the copper(II) complexes.

Free keywords: copper complex; imidazole; cyano; alcoholysis; structural analysis; DFT; QTAIM (Quantum Theory of Atoms in Molecules)

Contributing organizations

Ministry reporting: Yes

Reporting Year: 2019

JUFO rating: 1