Crystal Structures of Diaryliodonium Fluorides and their Implications for Fluorination Mechanisms

The radiofluorination of diaryliodonium salts is of value for producing radiotracers for positron emission tomography. We report crystal structures for two diaryliodonium fluorides. Whereas diphenyliodon um fluoride (1a) exists as a tetramer bridged by four fluoride ions, 2-methylphenyl(phenyl)iodonium fluoride (2a) forms a fluoride-bridged dimer that is further halogen-bonded to two other monomers. We discuss the topological relationships between the two and their implications for fluorination in solution. Both radiofluorination and NMR spectroscopy show that thermolysis of 2a gives 2-fluorotoluene and fluorobenzene in a 2 to 1 ratio that is in good agreement with the ratio observed from the radiofluorination of 2-methylphenyl(phenyl)iodonium chloride (2b). The constancy of the product ratio affirms that the fluorinations occur via the same two rapidly interconverting transition states whose energy difference dictates chemoselectivity. The quantum chemical studies with density functional theory at the level of B3LYP/DGDZVP provide deeper insight into the role of 'ortho effect' in the mechanism of fluorination. By utilizing the crystal structures of 1a and 2a, the mechanisms of fluoroarene formation from diaryliodonium fluorides in their monomeric, homodimeric, heterodimeric, and tetrameric states were also investigated. According to this analysis, we propose that oligomerization energy dictates whether the fluorination occurs through a monomeric or an oligomeric pathway.