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Halogen-bonded halogen(I) ion complexes (2023)

Ward, J. S., Truong, K.-N., Erdélyi, M., & Rissanen, K. (2023). Halogen-bonded halogen(I) ion complexes. In J. Reedijk, & K. R. Poeppelmeier (Eds.), Comprehensive Inorganic Chemistry III (Third Edition., pp. 586-601). Elsevier. https://doi.org/10.1016/B978-0-12-823144-9.00043-1

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Publication details

All authors or editorsWard, Jas S.; Truong, Khai-Nghi; Erdélyi, Mate; Rissanen, Kari

Parent publicationComprehensive Inorganic Chemistry III

Parent publication editorsReedijk, Jan; Poeppelmeier, Kenneth R.



EditionThird Edition

Publication year2023

Publication date01/03/2023

Pages range586-601


Publication countryNetherlands

Publication languageEnglish


Publication open accessNot open

Publication channel open access

Additional informationVolume 1 : Synthesis, Structure, and Bonding of Inorganic Molecular Systems, Volume editor: Risto S. Laitinen.
Chapter 1.12


Halogen bonding occurs between a positive region of a polarized halogen (X), most commonly with an iodine or bromine atom. The polarization, caused by an electron withdrawing group (R), induces electron deficiency onto the halogen atom, creating an electropositive region known as a σ-hole. This σ-hole then interacts with electron-rich nucleophiles (such as Lewis bases, B) forming a linear R–X···B halogen bond. When an electron is completely removed from a halogen, a halogen (I) ion (X+) is formed. A halogen(I) ion itself is highly reactive, but can be ‘trapped’ in between two Lewis bases creating a [L–X–L]+ 3-center, 4-electron halogen bond between the halogen(I) ion and two donor atoms of the Lewis bases (typically nitrogen). Halogen(I) complexes form a special family manifesting a strong halogen bond, which demonstrate good stability in both the solution and solid-states. An overview of the current state of halogen bonding of halogen(I) ion complexes is included, as well as the many advancements made to those fields in recent years.

Keywordscoordination complexeschemical bondshalogens

Free keywords3-Center-4-electron bond; bromonium; cation exchange; halogen bond; halonium ion; iodonium; Lewis base; N-donor ligand; NMR spectroscopy; S-donor ligand; silver(I) complex; solid-state; solution studies; X-ray crystallography

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Ministry reportingYes

Reporting Year2023

Preliminary JUFO rating2

Last updated on 2024-03-04 at 18:56