Probing Halogen Bonds by Scalar Couplings

Overview

Journal J Am Chem Soc

Publisher American Chemical Society

Specialty Chemistry

Date 2021 Jul 8

PMID 34236837

Citations 3

Authors

Bono Jimmink

Daniel Sethio

Lotta Turunen

Daniel von der Heiden

Mate Erdelyi

Affiliations

Soon will be listed here.

Abstract

As halogen bonding is a weak, transient interaction, its description in solution is challenging. We demonstrate that scalar coupling constants () are modulated by halogen bonding. The binding-induced magnitude change of one-bond couplings, even up to five bonds from the interaction site, correlates to the interaction strength. We demonstrate this using the NMR data of 42 halogen-bonded complexes in dichloromethane solution and by quantum chemical calculations. Our observation puts scalar couplings into the toolbox of methods for characterization of halogen bond complexes in solution and paves the way for their applicability for other types of weak σ-hole interactions.

Citing Articles

Relation between Halogen Bond Strength and IR and NMR Spectroscopic Markers.

Amonov A, Scheiner S Molecules. 2023; 28(22).

PMID: 38005241 PMC: 10673387. DOI: 10.3390/molecules28227520.

Principles and Applications of CFX Moieties as Unconventional Halogen Bond Donors in Medicinal Chemistry, Chemical Biology, and Drug Discovery.

Vaas S, Zimmermann M, Schollmeyer D, Stahlecker J, Engelhardt M, Rheinganz J J Med Chem. 2023; 66(15):10202-10225.

PMID: 37487500 PMC: 10424184. DOI: 10.1021/acs.jmedchem.3c00634.

Evidence for and evaluation of fluorine-tellurium chalcogen bonding.

Weiss R, Aubert E, Groslambert L, Pale P, Mamane V Chem Sci. 2023; 14(26):7221-7229.

PMID: 37416727 PMC: 10321537. DOI: 10.1039/d3sc00849e.

References

Laurence C, Graton J, Berthelot M, El Ghomari M . The diiodine basicity scale: toward a general halogen-bond basicity scale. Chemistry. 2011; 17(37):10431-44. DOI: 10.1002/chem.201101071. View

Chudzinski M, Taylor M . Correlations between computation and experimental thermodynamics of halogen bonding. J Org Chem. 2012; 77(7):3483-91. DOI: 10.1021/jo300279m. View

Barluenga J, Gonzalez-Bobes F, Murguia M, Ananthoju S, Gonzalez J . Bis(pyridine)iodonium tetrafluoroborate (IPy2BF4): a versatile oxidizing reagent. Chemistry. 2004; 10(17):4206-13. DOI: 10.1002/chem.200400136. View

Alkorta I, Elguero J, Del Bene J . Unusual acid-base properties of the P molecule in hydrogen-, halogen-, and pnicogen-bonded complexes. Phys Chem Chem Phys. 2016; 18(47):32593-32601. DOI: 10.1039/c6cp06474d. View

Hardegger L, Kuhn B, Spinnler B, Anselm L, Ecabert R, Stihle M . Systematic investigation of halogen bonding in protein-ligand interactions. Angew Chem Int Ed Engl. 2010; 50(1):314-8. DOI: 10.1002/anie.201006781. View

Del Bene J, Elguero J . One-bond spin-spin coupling constants of X-1H proton donors in complexes with X-H-Y hydrogen bonds, for X = 13C, 15N, 17O, and 19F: predictions, comparisons, and relationships among 1J X-H, 1K X-H, and X-H distances. J Am Chem Soc. 2004; 126(47):15624-31. DOI: 10.1021/ja0401545. View

Gilday L, Robinson S, Barendt T, Langton M, Mullaney B, Beer P . Halogen Bonding in Supramolecular Chemistry. Chem Rev. 2015; 115(15):7118-95. DOI: 10.1021/cr500674c. View

Krivdin L . Theoretical calculations of carbon-hydrogen spin-spin coupling constants. Prog Nucl Magn Reson Spectrosc. 2018; 108:17-73. DOI: 10.1016/j.pnmrs.2018.10.002. View

Riel A, Rowe R, Ho E, Carlsson A, Rappe A, Berryman O . Hydrogen Bond Enhanced Halogen Bonds: A Synergistic Interaction in Chemistry and Biochemistry. Acc Chem Res. 2019; 52(10):2870-2880. PMC: 7328900. DOI: 10.1021/acs.accounts.9b00189. View

10.

Erdelyi M . Halogen bonding in solution. Chem Soc Rev. 2012; 41(9):3547-57. DOI: 10.1039/c2cs15292d. View

11.

Politzer P, Murray J, Clark T . Halogen bonding and other σ-hole interactions: a perspective. Phys Chem Chem Phys. 2013; 15(27):11178-89. DOI: 10.1039/c3cp00054k. View

12.

Bruce D, Metrangolo P, Meyer F, Pilati T, Prasang C, Resnati G . Structure-function relationships in liquid-crystalline halogen-bonded complexes. Chemistry. 2010; 16(31):9511-24. DOI: 10.1002/chem.201000717. View

13.

Sun A, Lauher J, Goroff N . Preparation of poly(diiododiacetylene), an ordered conjugated polymer of carbon and iodine. Science. 2006; 312(5776):1030-4. DOI: 10.1126/science.1124621. View

14.

Sarwar M, Dragisic B, Salsberg L, Gouliaras C, Taylor M . Thermodynamics of halogen bonding in solution: substituent, structural, and solvent effects. J Am Chem Soc. 2010; 132(5):1646-53. DOI: 10.1021/ja9086352. View

15.

Saccone M, Catalano L . Halogen Bonding beyond Crystals in Materials Science. J Phys Chem B. 2019; 123(44):9281-9290. DOI: 10.1021/acs.jpcb.9b07035. View

16.

Carlsson A, Mehmeti K, Uhrbom M, Karim A, Bedin M, Puttreddy R . Substituent Effects on the [N-I-N](+) Halogen Bond. J Am Chem Soc. 2016; 138(31):9853-63. PMC: 4981895. DOI: 10.1021/jacs.6b03842. View

17.

Xu Y, Gabidullin B, Bryce D . Single-Crystal NMR Characterization of Halogen Bonds. J Phys Chem A. 2019; 123(29):6194-6209. DOI: 10.1021/acs.jpca.9b03587. View

18.

Perrin C, Erdelyi M . One-bond C-C coupling constants in ethers are not primarily determined by N-sigma delocalization. J Am Chem Soc. 2005; 127(17):6168-9. DOI: 10.1021/ja0504284. View

19.

Parisini E, Metrangolo P, Pilati T, Resnati G, Terraneo G . Halogen bonding in halocarbon-protein complexes: a structural survey. Chem Soc Rev. 2011; 40(5):2267-78. DOI: 10.1039/c0cs00177e. View

20.

Tupikina E, Denisov G, Antonov A, Tolstoy P . Unusual behaviour of the spin-spin coupling constant J upon formation of CHX hydrogen bond. Phys Chem Chem Phys. 2020; 22(4):1994-2000. DOI: 10.1039/c9cp05964d. View