Photoinitiated Reactions of Haloperfluorocarbons with Gold(I) Organometallic Complexes: Perfluoroalkyl Gold(I) and Gold(III) Complexes.

The study of perfluoroalkyl metal complexes is key to understand and improve metal-promoted perfluoroalkylation reactions. Herein, we report the synthesis of the first gold complexes with primary or secondary perfluoroalkyl ligands by photoinitiated reactions between AuI organometallic complexes and iodoperfluoroalkanes. Complexes of the types LAuRF (L=PPh3 or N,N-bis(2,6-diisopropylphenyl)imidazol-2-ylidene; RF =n-C4 F9 , n-C6 F13 , i-C3 F7 , c-C6 F11 ) and [Au(RF )(Ar)I(PPh3 )] (Ar=2,4,6-trimethylphenyl) have been isolated and characterized. Alkynes RF C≡CR were formed by reaction of Ph3 PAuC≡CR (R=Ph, nHex) with IRF (RF =n-C4 F9 , i-C3 F7 ). According to the evidences obtained, this transformation undergoes through a photoinitiated radical mechanism. AuIII complexes [Au(n-C4 F9 )(X)(Y)L] (X=Y=Cl, Br, I, Me; X=Me, Y=I) have been prepared or in situ generated, and their thermal or photochemical decomposition reactions have been studied.