Fluoroalkylation of a Methylplatinum(II) Complex under Photoirradiation

The UV irradiation of a mixture of PtMe2(cod) (cod = 1,5-cyclooctadiene) and n-C4F9I in a 1:12 molar ratio for 15 min produces Pt­(n-C4F9)2(cod) in 61% yield at room temperature. The reaction without irradiation, as reported previously, proceeds much more slowly; heating the mixture for 7 days at 50 °C forms PtMe­(n-C4F9)­(cod) in 9% yield and no Pt­(n-C4F9)2(cod). Pt­(n-C4F9)2(cod) is converted to complexes having chelating ligands, Pt­(n-C4F9)2(L) (L = dppe (1,2-bis­(diphenylphosphino)­ethane), dppp (1,3-bis­(diphenylphosphino)­propane), bpy (2,2′-bipyridine)). The photoassisted fluoroalkylation of PtMe­(n-C4F9)­(cod) also affords Pt­(n-C4F9)2(cod), while the monomethylplatinum complexes PtMe­(C6H4-4-F)­(cod) and PtClMe­(cod) react with n-C4F9I under photoirradiation to afford complexes with a perfluorobutyl ligand, Pt­(n-C4F9)­(C6H4-4-F)­(cod) and PtCl­(n-C4F9)­(cod), respectively. The above reactions do not provide isolable Pt­(IV) complexes, in contrast to the reactions of alkyl or fluoroalkyl iodides with diorganoplatinum­(II) complexes having dinitrogen ligands. The mechanism of the fluoroalkylation of Pt­(II) complexes under photoirradiation is discussed on the basis of the reaction products.