Solvated Nickel Complexes as Stoichiometric and Catalytic Perfluoroalkylation Agents**
Scott T. Shreiber, David A. Vicic
Abstract
Abstract The acetonitrile‐solvated [(MeCN)Ni(C 2 F 5 ) 3 ] − was prepared in order to compare and contrast its reactivity with the known [(MeCN)Ni(CF 3 ) 3 ] − towards organic electrophiles. Both [(MeCN)Ni(CF 3 ) 3 ] − and [(MeCN)Ni(C 2 F 5 ) 3 ] − successfully react with aryl iodonium and diazonium salts as well as alkynyl iodonium salts to give fluoroalkylated organic products. Electrochemical analysis of [(MeCN)Ni II (C 2 F 5 ) 3 ] − suggests that, upon electro‐oxidation to [(MeCN) n Ni III (C 2 F 5 ) 3 ], reductive homolysis of a perfluoroethyl radical occurs, with the concomitant formation of [(MeCN) 2 Ni II (C 2 F 5 ) 2 ]. Catalytic C−H trifluoromethylations of electron‐rich arenes were successfully achieved using either [(MeCN)Ni(CF 3 ) 3 ] − or the related [Ni(CF 3 ) 4 ] 2− . Stoichiometric reactions of the solvated nickel complexes reveal that “ligandless” nickel is exceptionally capable of serving as reservoir of CF 3 groups under catalytically relevant conditions.