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Activation of the Cyano Group at Imidazole via Copper Stimulated Alcoholysis

Department of Chemistry, University of Eastern Finland, P.O. Box 111, FI-80101 Joensuu, Finland
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Author to whom correspondence should be addressed.
Current address: Department of Chemistry, University of Jyväskylä, P.O. Box 35, FI-40014 Jyväskylä, Finland.
Inorganics 2019, 7(7), 87; https://doi.org/10.3390/inorganics7070087
Received: 19 June 2019 / Revised: 2 July 2019 / Accepted: 5 July 2019 / Published: 9 July 2019
(This article belongs to the Section Coordination Chemistry)
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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 24, 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. View Full-Text
Keywords: copper complex; imidazole; cyano; alcoholysis; structural analysis; DFT; QTAIM (Quantum Theory of Atoms in Molecules) copper complex; imidazole; cyano; alcoholysis; structural analysis; DFT; QTAIM (Quantum Theory of Atoms in Molecules)
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited (CC BY 4.0).

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Gayfullina, R.; Jääskeläinen, S.; Koshevoy, I.O.; Hirva, P. Activation of the Cyano Group at Imidazole via Copper Stimulated Alcoholysis. Inorganics 2019, 7, 87.

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