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
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
Published in
Chemistry : A European JournalAuthors
Date
2024Copyright
© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH
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.
...
Publisher
WileyISSN Search the Publication Forum
0947-6539Keywords
Publication in research information system
https://converis.jyu.fi/converis/portal/detail/Publication/194845978
Metadata
Show full item recordCollections
License
Related items
Showing items with similar title or keywords.
-
Ortho‐Substituent Effects on Halogen Bond Geometry for N‐Haloimide⋯2‐Substituted Pyridine Complexes
Yu, Shilin; Rautiainen, J. Mikko; Kumar, Parveen; Gentiluomo, Lorenzo; Ward, Jas S.; Rissanen, Kari; Puttreddy, Rakesh (Wiley-VCH Verlag, 2024)The nature of (imide)N–X⋯N(pyridine) halogen-bonded complexes formed by six N-haloimides and sixteen 2-substituted pyridines are studied using X-ray crystallography (68 crystal structures), Density Functional Theory (DFT) ... -
Iodine(I) and Silver(I) Complexes Incorporating 3-Substituted Pyridines
Rissanen, Kari; Ward, Jas S. (American Chemical Society (ACS), 2023)Building upon the first report of a 3-acetaminopyridine-based iodine(I) complex (1b) and its unexpected reactivity toward tBuOMe, several new 3-substituted iodine(I) complexes (2b–5b) have been synthesized. The iodine(I) ... -
Iodine(I) and Silver(I) Complexes of Benzoimidazole and Pyridylcarbazole Derivatives
Rissanen, Kari; Taipale, Essi; Truong, Khai-Nghi; Siepmann, Marcel (Wiley, 2021)The synthesis of iodine(I) complexes with either benzoimidazole or carbazole-derived sp 2 N -containing Lewis bases is described, as well as their corresponding silver(I) complexes. The addition of elemental iodine to the ... -
Linear bis‐Coordinate Silver(I) and Iodine(I) Complexes with R3R2R1N Tertiary Amines
Kumar, Parveen; Komulainen, Joonas; Frontera, Antonio; Ward, Jas S.; Schalley, Christoph; Rissanen, Kari; Puttreddy, Rakesh (Wiley-VCH Verlag, 2023)Homoleptic [L–I–L]⁺ iodine(I) complexes (where L is a R3R2R1N tertiary amine) were synthesized via the [L–Ag–L]⁺ → [L–I–L]⁺ cation exchange reaction. In solution, the amines form [R3R2R1N-Ag-NR1R2R3]⁺ ... -
Halogen bonding and mechanochemistry combined : synthesis, characterization, and application of N-iodosaccharin pyridine complexes
Schumacher, Christian; Truong, Khai-Nghi; Ward, Jas S.; Puttreddy, Rakesh; Rajala, Anssi; Lassila, Elias; Bolm, Carsten; Rissanen, Kari (Royal Society of Chemistry (RSC), 2024)Halogen-bonded complexes are utilized across a myriad of synthetic chemistry fields, with halogen(I) complexes such as Barluenga's reagent being ubiquitous in halogenation reactions. The preparation of Barluenga's reagent ...