A1 Journal article (refereed)
Strong N−X···O−N Halogen Bonds: Comprehensive Study on N‐Halosaccharin Pyridine N‐oxide Complexes (2019)

Puttreddy, Rakesh; Rautiainen, Mikko; Mäkelä, Toni; Rissanen, Kari (2019). Strong N−X···O−N Halogen Bonds: Comprehensive Study on N‐Halosaccharin Pyridine N‐oxide Complexes. Angewandte Chemie International Edition, 58 (51), 18610-18618. DOI: 10.1002/anie.201909759

JYU authors or editors

Publication details

All authors or editors: Puttreddy, Rakesh; Rautiainen, Mikko; Mäkelä, Toni; Rissanen, Kari

Journal or series: Angewandte Chemie International Edition

ISSN: 1433-7851

eISSN: 1521-3773

Publication year: 2019

Volume: 58

Issue number: 51

Pages range: 18610-18618

Publisher: Wiley-VCH Verlag

Publication country: Germany

Publication language: English

DOI: https://doi.org/10.1002/anie.201909759

Open Access: Publication channel is not openly available

Publication is parallel published (JYX): https://jyx.jyu.fi/handle/123456789/65912

Abstract

A detailed study of the strong N−X⋯−O−N+ (X = I, Br) halogen bonding interactions in solution and in the solid‐state reports 2×27 donor×acceptor complexes of N‐halosaccharins and pyridine N‐oxides (PyNO). Density Functional Theory (DFT) calculations were used to investigate the X···O halogen bond (XB) interaction energies in 54 complexes. The XB interaction energies were found to vary from –47.5 to –120.3 kJ mol–1, with the strongest N−I⋯−O−N+ XBs approaching those of 3‐center‐4‐electron [N–I–N]+ halogen‐bonded systems (∼160 kJ mol–1). Using a subset of 32 complexes, stabilized only through N−X···−O−N+ XB interactions, a simplified, computationally fast, electrostatic model to predict the X···O bond energies, was developed. Energies predicted by this simple model and much higher‐level theory DFT calculations agree excellently, illustrating the usefulness of the simplified electrostatic model. In solution, the 1H NMR association constants (KXB) determined in CDCl3 and acetone‐d6 vary from 2.0 x100 to >108 M‐1 following accurately the calculated σ‐hole nature on the donor halogen. The donor×acceptor complexation enthalpies calculated in CHCl3 using polarized continuum model very between –38.4 and –77.5 kJ mol–1 and correlate well with the pKXB values determined by 1H NMR in CDCl3 indicating the formation of strong and robust 1:1 XB complexes in solution. In X‐ray crystal structures, the N‐iodosaccharin‐PyNO complexes manifest short normalized interaction ratios (RXB) between 0.65 – 0.67 for the N−I⋯−O−N+ halogen bond.

Keywords: chemical bonds

Free keywords: halogen bonds

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Ministry reporting: Yes

Reporting Year: 2019

JUFO rating: 3