A1 Journal article (refereed)
Ortho‐Substituent Effects on Halogen Bond Geometry for N‐Haloimide⋯2‐Substituted Pyridine Complexes (2024)

Yu, S., Rautiainen, J. M., Kumar, P., Gentiluomo, L., Ward, J. S., Rissanen, K., & Puttreddy, R. (2024). Ortho‐Substituent Effects on Halogen Bond Geometry for N‐Haloimide⋯2‐Substituted Pyridine Complexes. Advanced Science, 11(6), Article 2307208. https://doi.org/10.1002/advs.202307208

JYU authors or editors

Publication details

All authors or editors: Yu, Shilin; Rautiainen, J. Mikko; Kumar, Parveen; Gentiluomo, Lorenzo; Ward, Jas S.; Rissanen, Kari; Puttreddy, Rakesh

Journal or series: Advanced Science

ISSN: 2198-3844

eISSN: 2198-3844

Publication year: 2024

Publication date: 07/12/2023

Volume: 11

Issue number: 6

Article number: 2307208

Publisher: Wiley-VCH Verlag

Publication country: Germany

Publication language: English

DOI: https://doi.org/10.1002/advs.202307208

Publication open access: Openly available

Publication channel open access: Open Access channel

Publication is parallel published (JYX): https://jyx.jyu.fi/handle/123456789/92306

Abstract

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) (86 complexation energies), and NMR spectroscopy (90 association constants). Strong halogen bond (XB) donors such as N-iodosuccinimide form only 1:1 haloimide:pyridine crystalline complexes, but even stronger N-iodosaccharin forms 1:1 haloimide:pyridine and three other distinct complexes. In 1:1 haloimide:pyridine crystalline complexes, the haloimide's N─X bond exhibits an unusual bond bending feature that is larger for stronger N-haloimides. DFT complexation energies (ΔEXB) for iodoimide–pyridine complexes range from −44 to −99 kJ mol−1, while for N-bromoimide–pyridine, they are between −31 and −77 kJ mol−1. The ΔEXB of I⋯N XBs in 1:1 iodosaccharin:pyridine complexes are the largest of their kind, but they are substantially smaller than those in [bis(saccharinato)iodine(I)]pyridinium salts (−576 kJ mol−1), formed by N-iodosaccharin and pyridines. The NMR association constants and ΔEXB energies of 1:1 haloimide:pyridine complexes do not correlate as these complexes in solution are heavily influenced by secondary interactions, which DFT studies do not account for. Association constants follow the σ-hole strengths of N-haloimides, which agree with DFT and crystallography data. The haloimide:2-(N,N-dimethylamino)pyridine complex undergoes a halogenation reaction resulting in 5-iodo-2-dimethylaminopyridine.

Keywords: halogens; saccharin

Free keywords: halogen bond; haloimide; ortho; saccharin; sigma hole

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Ministry reporting: Yes

VIRTA submission year: 2023

JUFO rating: 1