Solvated Nickel Complexes as Stoichiometric and Catalytic Perfluoroalkylation Agents**

Shreiber, Scott T.; Vicic, David A.

doi:10.1002/ange.202104559

Title: Solvated Nickel Complexes as Stoichiometric and Catalytic Perfluoroalkylation Agents**

Journal Article · 09 July 2021 · Angewandte Chemie

DOI: https://doi.org/10.1002/ange.202104559 · OSTI ID:1806604

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Department of Chemistry Lehigh University 6 E. Packer Avenue Bethlehem PA 18015 USA

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.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0009363

OSTI ID:: 1806604

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 33 Vol. 133; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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