A3 Book section, Chapters in research books
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

JYU authors or editors

Publication details

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

Parent publication: Comprehensive Inorganic Chemistry III

Parent publication editors: Reedijk, Jan; Poeppelmeier, Kenneth R.

ISBN: 978-0-12-823144-9

eISBN: 978-0-12-823153-1

Edition: Third Edition

Publication year: 2023

Publication date: 01/03/2023

Pages range: 586-601

Publisher: Elsevier

Publication country: Netherlands

Publication language: English

DOI: https://doi.org/10.1016/B978-0-12-823144-9.00043-1

Publication open access: Not open

Publication channel open access:

Additional information: Volume 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.

Keywords: coordination complexes; chemical bonds; halogens

Free keywords: 3-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 reporting: Yes

Reporting Year: 2023

Preliminary JUFO rating: 2

Last updated on 2023-03-10 at 10:44