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Carbonyl Hypoiodites as Extremely Strong Halogen Bond Donors.

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.

SUBMITTER: Yu S

PROVIDER: S-EPMC8518949 | biostudies-literature | 2021 Sep

REPOSITORIES: biostudies-literature

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Carbonyl Hypoiodites as Extremely Strong Halogen Bond Donors.

Yu Shilin S Ward Jas S JS Truong Khai-Nghi KN Rissanen Kari K

Angewandte Chemie (International ed. in English) 20210824 38

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<sup>-</sup> ⋅⋅⋅I-N<sup>+</sup> ion-pair (salt) wi ...[more]

PMID: 34268851

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