Carbonyl Hypoiodites as Extremely Strong Halogen Bond Donors
Yu, S., Ward, J. S., Truong, K.-N., & Rissanen, K. (2021). Carbonyl Hypoiodites as Extremely Strong Halogen Bond Donors. Angewandte Chemie, 60(38), 20739-20743. https://doi.org/10.1002/anie.202108126
Published inAngewandte Chemie
© 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH
Neutral halogen-bonded O−I−N complexes were prepared from in situ formed carbonyl hypoiodites and aromatic organic bases. The carbonyl hypoiodites have a strongly polarized iodine atom with larger σ-holes than any known uncharged halogen bond donor. Modulating the Lewis basicity of the selected pyridine derivatives and carboxylates leads to halogen-bonded complexes where the classical O−I⋅⋅⋅N halogen bond transforms more into a halogen-bonded COO−⋅⋅⋅I−N+ ion-pair (salt) with an asymmetric O−I−N moiety. X-ray analyses, NMR studies, and calculations reveal the halogen bonding geometries of the carbonyl hypoiodite-based O−I−N complexes, confirming that in the solid-state the iodine atom is much closer to the N-atom of the pyridine derivatives than its original position at the carboxylate O-atom.
Publication in research information system
MetadataShow full item record
Related funder(s)Academy of Finland
Funding program(s)Academy Project, AoF
Additional information about fundingWe are grateful for financial support from the Academy of Finland (K.R.: grant no. 317259), the Finnish Cultural Foundation Central Fund (J.S.W.: grant no. 00201148), the Magnus Ehrnrooth Foundation (J.S.W.), and the University of Jyväskylä.
Showing items with similar title or keywords.
Anyfanti, Goulielmina; Bauzá, Antonio; Gentiluomo, Lorenzo; Rodrigues, João; Portalone, Gustavo; Frontera, Antonio; Rissanen, Kari; Puttreddy, Rakesh (Frontiers Media SA, 2021)Hexamethylenetetramine (HMTA) and N-haloimides form two types of short (imide)X···N and X–X···N (X = Br, I) halogen bonds. Nucleophilic substitution or ligand-exchange reaction on the peripheral X of X–X···N with the ...
Kramer, Eric; Yu, Shilin; Ward, Jas S.; Rissanen, Kari (Royal Society of Chemistry (RSC), 2021)Four bis(O–I–N) compounds have been synthesised from various dihypoiodites and 4-ethylpyridine. The compounds were characterised in both the solution and solid states by NMR spectroscopy (1H, 15N), X-ray diffraction, and ...
Topic, Filip; Puttreddy, Rakesh; Rautiainen, Mikko; Tuononen, Heikki; Rissanen, Kari (Royal Society of Chemistry, 2017)The X-ray structures of the first co-crystals where the three oxygen lone pairs in N-oxides are fully utilized for tridentate C–I⋯O−–N+ halogen bonding with 1,ω-diiodoperfluoroalkanes are reported, studied computationally, ...
Reactivity of 4-Aminopyridine with Halogens and Interhalogens : Weak Interactions Supported Networks of 4-Aminopyridine and 4-Aminopyridinium Kukkonen, Esa Petteri; Malinen, Henri; Haukka, Matti; Konu, Jari (American Chemical Society, 2019)The reaction of 4-aminopyridine (4-AP) with ICl in a 1:1 molar ratio in CH2Cl2 produced the expected charge-transfer complex [4-NH2-1λ4-C5H4N-1-ICl] (1·ICl) and the ionic species [(4-NH2-1λ4-C5H4N)2-1μ-I+][Cl–] (2·Cl–) in ...
Turunen, Lotta (University of Jyväskylä, 2017)This thesis describes the design, synthesis and characterization of supramolecular halogen-bonded capsules and cages from multivalent ligands. In the first part of the thesis, an overview to halogen bonding is provided. ...