The halogen bonding of halonium ions

NAISS 2023/5-392


NAISS Medium Compute

Principal Investigator:

Mate Erdelyi


Uppsala universitet

Start Date:


End Date:


Primary Classification:

10405: Organic Chemistry

Secondary Classification:

10407: Theoretical Chemistry



My group has investigated the halogen bond of halonium ions since OVER a decade, which work has resulted in a number of publications (for example ChemComm 2012, 48, 1458, JACS 2012, 134, 5706, Cryst Eng Comm 2013, 15, 3087, Chem. Sci. 2014, 5, 3226-3233, Chem. Sci. 2015, 6, 3746-3756, J. Am. Chem. Soc. 2016, 138, 9853, J. Am Chem. Soc. 2018, 140, 13503, J. Am. Chem. Soc. 2018, 140, 17571, Angew. Chem. Int. Ed. 2019, 58, 9012, Chem. Commun. 2020, 56, 14431; J. Chem. Theory Comput. 2020, 16, 7690; Chem. Commun. 2020, 56, 9671; Chem. Sci. 2020, 11, 7979; Chem. Soc. Rev. 2020, 49, 2688; Chem. Eur. J. 2021, DOI: 10.1002/chem.202102575; J. Am. Chem. Soc. 2021,143, 10695; Bull. Chem. Soc. Jpn. 2021, 94, 191, ChemComm 2022, 58, 4977; ACS Catalysis 2022, 12, 7210etc). These studies focus on experimental - spectroscopic studies, but use computations for prediction, design and data interpretation. Computations are also needed for the evaluation of properties (minor changes i bond length or electron distribution) that we cannot measure by NMR. We have benchmarked computational methods for this specific type of halogen bonds, and initiated computations addressing the mechanism of halogen transfer processes. We have also developed new strategies to detect and characterize very weak halogen bonds, and to use this in developing environmentally friendly synthetic procedures (halogen bond activation in gold catalysis, for instance). We wish to proceed with this work, focusing on continuously chiral ligands and organic frameworks that have a high potential for applicability in asymmetric halogenation reactions. The project will include DFT calculations using Gaussian, including geometry optimizations, potential energy scans, estimation of NMR chemical shifts, etc. It will also make use of Monte Carlo conformational searches combined with molecular mechanics minimizations. The project is related to our previous work in the projects HPC2N-2013-019, HPCN-2014-2-21, SNIC 2020/5-435, SNIC 20215-359 and SNIC 2022/5-431. It is our flagship project that over the past decade has delivered a large number of high impact publications ( JACS, Angewandte, Chemical Science, etc) and ground breaking results that have pushed the frontiers of the research field. We wish to continue this work.