Solvated Nickel Complexes as Stoichiometric and Catalytic Perfluoroalkylation Agents**

The acetonitrile-solvated [(MeCN)Ni(C2F5)(3)](-) was prepared in order to compare and contrast its reactivity with the known [(MeCN)Ni(CF3)(3)](-) towards organic electrophiles. Both [(MeCN)Ni(CF3)(3)](-) and [(MeCN)Ni(C2F5)(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(C2F5)(3)](-) suggests that, upon electro-oxidation to [(MeCN)(n)Ni-III(C2F5)(3)], reductive homolysis of a perfluoroethyl radical occurs, with the concomitant formation of [(MeCN)(2)Ni-II(C2F5)(2)]. Catalytic C-H trifluoromethylations of electron-rich arenes were successfully achieved using either [(MeCN)Ni(CF3)(3)](-) or the related [Ni(CF3)(4)](2-). Stoichiometric reactions of the solvated nickel complexes reveal that ligandless nickel is exceptionally capable of serving as reservoir of CF3 groups under catalytically relevant conditions.

Automated summary

The solvated nickel complexes react with organic electrophiles to synthesize fluoroalkylated organic products. Electrochemical analysis reveals that nickel complexes can act as reservoirs of CF3 groups under certain conditions.