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 Au organometallic complexes and iodoperfluoroalkanes. Complexes of the types LAuR (L=PPh or N,N-bis(2,6-diisopropylphenyl)imidazol-2-ylidene; R =n-C F , n-C F , i-C F , c-C F ) and [Au(R )(Ar)I(PPh )] (Ar=2,4,6-trimethylphenyl) have been isolated and characterized. Alkynes R C≡CR were formed by reaction of Ph PAuC≡CR (R=Ph, nHex) with IR (R =n-C F , i-C F ). According to the evidences obtained, this transformation undergoes through a photoinitiated radical mechanism. Au complexes [Au(n-C F )(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.