Nucleophilic Fluorination of closo- Decaborate Iodonium Derivatives

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-B10H9IPh] 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.