Details

Autor(en) / Beteiligte

• Portugués, Alejandro
• López‐García, Inmaculada
• Jiménez‐Bernad, Javier
• Bautista, Delia
• Gil‐Rubio, Juan

Titel

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

Ist Teil von

• Chemistry : a European journal, 2019-12, Vol.25 (68), p.15535-15547

Ort / Verlag

Germany: Wiley Subscription Services, Inc

Erscheinungsjahr

2019

Quelle

Wiley Online Library - AutoHoldings Journals

Beschreibungen/Notizen

• 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‐C4F9, n‐C6F13, i‐C3F7, c‐C6F11) and [Au(RF)(Ar)I(PPh3)] (Ar=2,4,6‐trimethylphenyl) have been isolated and characterized. Alkynes RFC≡CR were formed by reaction of Ph3PAuC≡CR (R=Ph, nHex) with IRF (RF=n‐C4F9, i‐C3F7). According to the evidences obtained, this transformation undergoes through a photoinitiated radical mechanism. AuIII complexes [Au(n‐C4F9)(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. Enlightened: Irradiation with a mild light source (402 nm LED) can activate reactions between iodoperfluoroalkanes and AuI organometallic complexes. These reactions proceed through a radical mechanism and have led to the first isolated AuI and AuIII complexes containing perfluoroalkyl chains, including rare perfluorocyclohexyl metal complexes.