A1 Journal article (refereed)
A “nucleophilic” iodine in a halogen-bonded iodonium complex manifests an unprecedented I+···Ag+ interaction (2021)

Yu, S., Kumar, P., Ward, J. S., Frontera, A., & Rissanen, K. (2021). A “nucleophilic” iodine in a halogen-bonded iodonium complex manifests an unprecedented I+···Ag+ interaction. Chem, 7(4), 948-958. https://doi.org/10.1016/j.chempr.2021.01.003

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Publication details

All authors or editors: Yu, Shilin; Kumar, Parveen; Ward, Jas S.; Frontera, Antonio; Rissanen, Kari

Journal or series: Chem

ISSN: 2451-9294

eISSN: 2451-9294

Publication year: 2021

Volume: 7

Issue number: 4

Pages range: 948-958

Publisher: Elsevier BV

Publication country: Netherlands

Publication language: English

DOI: https://doi.org/10.1016/j.chempr.2021.01.003

Publication open access: Not open

Publication channel open access: 

Abstract

When an electron is removed from a halogen atom, it forms a halenium ion X+ (X = I, Br, Cl). In halogen bonding (XB), X+ is considered as a strong XB donor, and when interacting with two XB acceptors (e.g., pyridine), it forms a halonium XB complex with a [N–I–N] three-center-four-electron bond with the two XB acceptors. An unprecedented I+···Ag+ interaction occurs between a [L1–I–L1]+ halogen-bonded complex and a [L2–Ag–L2]+ complex in which the iodonium ion acts like a nucleophile and donates electrons to the silver(I) cation. The X-ray diffraction analysis reveals a short contact [3.4608(3) Å] between the I+ and Ag+ cations, and ITC measurements give a ΔG of −6.321 kcal/mol and Ka∼37,000 M−1 for the 1:1 complex. The DFT computational study on the nature of the I+···Ag+ interaction indicates that the I+ is nucleophilic in character, manifesting an unusual and strongly attractive interaction between the I+ and Ag+ cations.

Keywords: coordination complexes; halogens; iodine; silver; chemical bonds

Free keywords: halonium ion; halogen bonding; nucleophile; I+···Ag+ interaction; X-ray structure

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Ministry reporting: Yes

Reporting Year: 2021

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