Strong N−X···O−N Halogen Bonds: Comprehensive Study on N‐Halosaccharin Pyridine N‐oxide Complexes
Puttreddy, R., Rautiainen, M., Mäkelä, T., & Rissanen, K. (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. https://doi.org/10.1002/anie.201909759
Published inAngewandte Chemie International Edition
DisciplineOrgaaninen kemiaNanoscience CenterEpäorgaaninen ja analyyttinen kemiaOrganic ChemistryNanoscience CenterInorganic and Analytical Chemistry
© 2019 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim
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. ...
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Related funder(s)Academy of Finland
Funding program(s)Postdoctoral Researcher, AoF
Additional information about fundingThe authors gratefully acknowledge financial support from the Academy of Finland (RP grant no. 298817), grants of computational resources from the Finnish Grid and Cloud Infrastructure (urn:nbn:fi:research-infras-2016072533) and CSC –IT Center for Science, and the University of Jyväskylä.The help of Prof. Dr. Christoph Schalley and M.Sc. Henrik Hupatz (Freie Universität Berlin, Germany), Dr. Alexander S. Novikov with the computational studies (Saint Petersburg State University, Russia), and Prof. Dr. Heikki Tuononen(University of Jyväskylä, Finland)forvaluable suggestions for the 1stversion of the manuscript aregratefully acknowledged. ...
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