Electrophilic fluorination of organoplatinum(II) iodides: Iodine and platinum atoms as competing fluorination sites

A series of diphosphine Pt(II) aryl iodo complexes were reacted with XeF ₂ to cleanly produce the corresponding Pt(II) difluoro complexes and free iodoarenes. However, when aryl ligands bearing fluoro substituents in the ortho positions were used, the formation of the corresponding Pt(II) aryl fluoro complexes was observed in the reaction with XeF ₂. In the case of the Pt-C ₆F ₅ complex, the products of the fluoride-for-iodide exchange were the only products observed by means of ³¹P and ¹⁹F NMR spectroscopy. The experimental and theoretical studies suggest that the formation of iodine-fluorine bond may accompany this transformation. The plausible "I-F" species could be trapped by electron-richer organoplatinum complexes to give a Pt(IV) transient which subsequently eliminates the corresponding aryl iodide. Hence, in some cases a pathway involving an attack of XeF ₂ at the iodo ligand of Pt(II) aryl iodo complexes to generate I-F species can be operative in addition to or instead of the XeF ₂ attack at the metal center. Our DFT studies demonstrate that the electrophilic attacks of XeF ₂ at both sites, platinum and iodide, can be competitive.