Solvated Nickel Complexes as Stoichiometric and Catalytic Perfluoroalkylation Agents

01 April 2021, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


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)NiII(C2F5)3]– suggests that, upon electro-oxidation to [(MeCN)nNi(C2F5)3], reductive homolysis of a perfluoroethyl radical occurs, with the concomitant formation of [(MeCN)Ni(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 anions or radicals under catalytically relevant conditions.



Supplementary materials

Solvated Nickel SI


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