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.

Basic information

Original name

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

Authors

PARVEEN, Kumar (356 India), Rautiainen MIKKO (246 Finland), Jan NOVOTNÝ (203 Czech Republic, belonging to the institution), Ward JAS S. (826 United Kingdom of Great Britain and Northern Ireland), Radek MAREK (203 Czech Republic, guarantor, belonging to the institution), Rissanen KARI (246 Finland) and Puttreddy RAKESH (246 Finland)

Edition

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

Other information

Language

English

Type of outcome

Článek v odborném periodiku

Field of Study

10400 1.4 Chemical sciences

Country of publisher

Germany

Confidentiality degree

není předmětem státního či obchodního tajemství

References:

DOI: 10.1002/chem.202303643

Impact factor

Impact factor: 4.300 in 2022

Organization unit

Faculty of Science

DOI

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

UT WoS

001143279900001

Keywords in English

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

Abstract

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.

Links

GA21-06991S, research and development project

Name: Relativistické efekty v paramagnetické NMR spektroskopii (Acronym: RELMAG)

Investor: Czech Science Foundation, Relativistic Effects in Paramagnetic NMR Spectroscopy

90254, large research infrastructures

Name: e-INFRA CZ II

Citovat

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. 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.

@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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