A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä
The impact of ortho‐substituents on Bonding in Silver(I) and Halogen(I) complexes of 2‐Mono‐ and 2,6‐Disubstituted Pyridines : An In‐depth Experimental and Theoretical Study (2024)

Kumar, P., Rautiainen, J. M., Novotny, J., Ward, J. S., Marek, R., Rissanen, K., & Puttreddy, R. (2024). The impact of ortho‐substituents on Bonding in Silver(I) and Halogen(I) complexes of 2‐Mono‐ and 2,6‐Disubstituted Pyridines : An In‐depth Experimental and Theoretical Study. Chemistry : A European Journal, 30, Article e202303643. https://doi.org/10.1002/chem.202303643

JYU-tekijät tai -toimittajat

Kumar, Parveen
Rautiainen, Mikko
Ward, James
Rissanen, Kari
Puttreddy, Rakesh

Julkaisun tiedot

Julkaisun kaikki tekijät tai toimittajat: Kumar, Parveen; Rautiainen, J. Mikko; Novotny, Jan; Ward, Jas S.; Marek, Radek; Rissanen, Kari; Puttreddy, Rakesh

Lehti tai sarja: Chemistry : A European Journal

ISSN: 0947-6539

eISSN: 1521-3765

Julkaisuvuosi: 2024

Ilmestymispäivä: 06.12.2023

Volyymi: 30

Artikkelinumero: e202303643

Kustantaja: Wiley

Julkaisumaa: Saksa

Julkaisun kieli: englanti

DOI: https://doi.org/10.1002/chem.202303643

Julkaisun avoin saatavuus: Avoimesti saatavilla

Julkaisukanavan avoin saatavuus: Osittain avoin julkaisukanava

Julkaisu on rinnakkaistallennettu (JYX): https://jyx.jyu.fi/handle/123456789/94299

Tiivistelmä

The coordination nature of 2-mono- and 2,6-disubstituted pyridines with electron-withdrawing halogen and electron-donating methyl groups for [N–X–N]⁺ (X =I, Br) complexations have been studied using 15N NMR, X-ray crystallography, and Density Functional Theory (DFT) calculations. The 15N NMR chemical shifts reveal iodine(I) and bromine(I) prefer to form complexes with 2-substituted pyridines and only 2,6-dimethylpyridine. The crystalline halogen(I) complexes of 2-substituted pyridines were characterized by using X-ray diffraction analysis, but 2,6-dihalopyridines were unable to form stable crystalline halogen(I) complexes due to the lower nucleophilicity of the pyridinic nitrogen. In contrast, the halogen(I) complexes of 2,6-dimethylpyridine, which has a more basic nitrogen, are characterized by X-crystallography, which complements the 15N NMR studies. DFT calculations reveal that the bond energies for iodine(I) complexes vary between -291 and -351 kJmol-1 and for bromine between -370 and -427 kJmol-1. The bond energies of halogen(I) complexes of 2-halopyridines with more nucleophilic nitrogen are 66 - 76 kJmol-1 larger than those of analogous 2,6-dihalopyridines with less nucleophilic nitrogen. The experimental and DFT results show that the electronic influence of ortho-halogen substituents on pyridinic nitrogen leads to a completely different preference for the coordination bonding of halogen(I) ions, providing new insights into bonding in halogen(I) chemistry.

YSO-asiasanat: halogeenit; kemia

Liittyvät organisaatiot

OKM-raportointi: Kyllä

VIRTA-lähetysvuosi: 2023

JUFO-taso: 2