Nucleophilic fluorination of closo-decaborate iodonium derivatives
Publikationstyp
Journal Article
Date Issued
2026-06-04
Sprache
English
Author(s)
Neumolotov, Nikolay
Voinova, Vera
Klyukin, Ilya N.
Selivanov, Nikita
Kubasov, Alexey
Zhdanov, Andrey P.
Lipengolts, Alexey
Zhizhin, Konstantin Yu
Kuznetsov, Nikolay
Volume
65
Issue
24
Start Page
13410
End Page
13427
Citation
Inorganic Chemistry 65 (24): 13410-13427
Publisher DOI
Scopus ID
Publisher
American Chemical Society (ACS)
New fluoroderivatives of the closo-decaborate anion with the composition [1,10-B₁₀H₈FX]ⁿ⁻ (where X = IPh, Pyridine, I, Br, Cl, F, OH, CN) as well as [1-F, 6-NH₃B₁₀H₈]⁻ have been obtained. It was found that uncharged bisphenyliodonium derivative [1,10-(IPh)₂B₁₀H₈]⁰ undergoes a nucleophilic substitution with the [K(18-crown-6)]⁺F⁻ complex to form monofluoro derivative [1-IPh, 10-FB₁₀H₈]⁻, whereas the anionic Bu₄N[1-B₁₀H₉Ph] does not react with the complex. This charge-dependent reactivity, as well as solvent effects, was explained using DFT and QTAIM calculations, revealing the crucial role of iodine sigma-hole availability and competitive solvation. The structures of the key products were confirmed by multinuclear NMR spectroscopy and single-crystal X-ray diffraction.
Subjects
Derivatives
Fluorine compounds
Halogenation
Negative ions
Single crystals
X ray diffraction
DDC Class
540: Chemistry