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Photoinitiated Reactions of Haloperfluorocarbons with Gold(I) Organometallic Complexes: Perfluoroalkyl Gold(I) and Gold(III) Complexes
Author(s) -
Portugués Alejandro,
LópezGarcía Inmaculada,
JiménezBernad Javier,
Bautista Delia,
GilRubio Juan
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201903058
Subject(s) - chemistry , metal , thermal decomposition , decomposition , organometallic chemistry , stereochemistry , medicinal chemistry , crystallography , organic chemistry , crystal structure
Abstract 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 I organometallic complexes and iodoperfluoroalkanes. Complexes of the types LAuR F (L=PPh 3 or N , N ‐bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene; R F = n ‐C 4 F 9 , n ‐C 6 F 13 , i ‐C 3 F 7 , c ‐C 6 F 11 ) and [Au(R F )(Ar)I(PPh 3 )] (Ar=2,4,6‐trimethylphenyl) have been isolated and characterized. Alkynes R F C≡CR were formed by reaction of Ph 3 PAuC≡CR (R=Ph, n Hex) with IR F (R F = n ‐C 4 F 9 , i ‐C 3 F 7 ). According to the evidences obtained, this transformation undergoes through a photoinitiated radical mechanism. Au III complexes [Au( n ‐C 4 F 9 )(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.