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Carbonyl Hypoiodites as Extremely Strong Halogen Bond Donors
Author(s) -
Yu Shilin,
Ward Jas S.,
Truong KhaiNghi,
Rissanen Kari
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202108126
Subject(s) - chemistry , halogen , halogen bond , pyridine , moiety , atom (system on chip) , lewis acids and bases , carboxylate , iodine , crystallography , photochemistry , medicinal chemistry , stereochemistry , organic chemistry , catalysis , alkyl , computer science , embedded system
Abstract 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.