A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä
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-tekijät tai -toimittajat

Julkaisun tiedot

Julkaisun kaikki tekijät tai toimittajat: Gayfullina, Rezeda; Jääskeläinen, Sirpa; Koshevoy, Igor O.; Hirva, Pipsa

Lehti tai sarja: Inorganics

eISSN: 2304-6740

Julkaisuvuosi: 2019

Volyymi: 7

Lehden numero: 7

Artikkelinumero: 87

Kustantaja: MDPI AG

Julkaisumaa: Sveitsi

Julkaisun kieli: englanti

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

Julkaisun avoin saatavuus: Avoimesti saatavilla

Julkaisukanavan avoin saatavuus: Kokonaan avoin julkaisukanava

Julkaisu on rinnakkaistallennettu (JYX): https://jyx.jyu.fi/handle/123456789/65767

Tiivistelmä

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.

Vapaat asiasanat: epäorgaaninen kemia

Liittyvät organisaatiot

OKM-raportointi: Kyllä

Raportointivuosi: 2019

JUFO-taso: 1