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

J 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

PARVEEN, Kumar, Rautiainen MIKKO, Jan NOVOTNÝ, Ward JAS S., Radek MAREK et. al.

Základní údaje

Originální název

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

Autoři

PARVEEN, Kumar (356 Indie), Rautiainen MIKKO (246 Finsko), Jan NOVOTNÝ (203 Česká republika, domácí), Ward JAS S. (826 Velká Británie a Severní Irsko), Radek MAREK (203 Česká republika, garant, domácí), Rissanen KARI (246 Finsko) a Puttreddy RAKESH (246 Finsko)

Vydání

Chemistry - A European Journal, Wiley, 2024, 0947-6539

Další údaje

Jazyk

angličtina

Typ výsledku

Článek v odborném periodiku

Obor

10400 1.4 Chemical sciences

Stát vydavatele

Německo

Utajení

není předmětem státního či obchodního tajemství

Odkazy

DOI: 10.1002/chem.202303643

Impakt faktor

Impact factor: 4.300 v roce 2022

Organizační jednotka

Přírodovědecká fakulta

DOI

http://dx.doi.org/10.1002/chem.202303643

UT WoS

001143279900001

Klíčová slova anglicky

silver(I); halogen(I); pyridine; NMR shift; 15N NMR; DFT; relativistic effects; XRD; diffraction

Štítky

rivok

Příznaky

Mezinárodní význam, Recenzováno

Změněno: 19. 3. 2024 08:20, prof. RNDr. Radek Marek, Ph.D.

Anotace

V originále

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.

Návaznosti

GA21-06991S, projekt VaV

Název: Relativistické efekty v paramagnetické NMR spektroskopii (Akronym: RELMAG)

Investor: Grantová agentura ČR, Relativistické efekty v paramagnetické NMR spektroskopii

90254, velká výzkumná infrastruktura

Název: e-INFRA CZ II

Citovat

PARVEEN, Kumar, Rautiainen MIKKO, Jan NOVOTNÝ, Ward JAS S., Radek MAREK, Rissanen KARI a 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. Chemistry - A European Journal. Wiley, 2024, roč. 30, č. 13, s. 1-10. ISSN 0947-6539. Dostupné z: https://dx.doi.org/10.1002/chem.202303643.

@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 a 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, roč.~30, č.~13, s.~1-10. ISSN~0947-6539. Dostupné z: https://dx.doi.org/10.1002/chem.202303643.

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