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Solvated Nickel Complexes as Stoichiometric and Catalytic Perfluoroalkylation Agents

preprint
submitted on 31.03.2021, 16:26 and posted on 01.04.2021, 12:41 by Scott T. Shreiber, David Vicic

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.

Funding

Fundamental Studies Focused on the Organometallic Chemistry of Earth Abundant Metals

Basic Energy Sciences

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History

Email Address of Submitting Author

vicic@lehigh.edu

Institution

Lehigh University

Country

USA

ORCID For Submitting Author

0000-0002-4990-0355

Declaration of Conflict of Interest

no conflict of interest

Exports

ChemRxiv

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