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@article{2346797,
author = {Parveen, Kumar and Mikko, Rautiainen and Novotný, Jan and Jas S., Ward and Marek, Radek and Kari, Rissanen and Rakesh, Puttreddy},
article_number = {13},
doi = {http://dx.doi.org/10.1002/chem.202303643},
keywords = {silver(I); halogen(I); pyridine; NMR shift; 15N NMR; DFT; relativistic effects; XRD; diffraction},
language = {eng},
issn = {0947-6539},
journal = {Chemistry - A European Journal},
title = {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},
url = {http://dx.doi.org/10.1002/chem.202303643},
volume = {30},
year = {2024}
}
TY - JOUR
ID - 2346797
AU - Parveen, Kumar - Mikko, Rautiainen - Novotný, Jan - Jas S., Ward - Marek, Radek - Kari, Rissanen - Rakesh, Puttreddy
PY - 2024
TI - 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
JF - Chemistry - A European Journal
VL - 30
IS - 13
SP - 1-10
EP - 1-10
PB - Wiley
SN - 09476539
KW - silver(I)
KW - halogen(I)
KW - pyridine
KW - NMR shift
KW - 15N NMR
KW - DFT
KW - relativistic effects
KW - XRD
KW - diffraction
UR - http://dx.doi.org/10.1002/chem.202303643
N2 - 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 kJ mol-1 and for bromine between -370 and -427 kJ mol-1. The bond energies of halogen(I) complexes of 2-halopyridines with more nucleophilic nitrogen are 66 - 76 kJ mol-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.
ER -
PARVEEN, Kumar, Rautiainen MIKKO, Jan NOVOTNÝ, Ward JAS S., Radek MAREK, Rissanen KARI and Puttreddy RAKESH. 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. \textit{Chemistry - A European Journal}. Wiley, 2024, vol.~30, No~13, p.~1-10. ISSN~0947-6539. Available from: https://dx.doi.org/10.1002/chem.202303643.
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