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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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