A T-shaped Ni[κ2-(CF2)4–] NHC complex: unusual Csp3–F and M–CF bond functionalization reactions. Issue 11 (6th August 2015)

• Record Type: Journal Article
• Authors: Andrella, Nicholas O.; Sicard, Alexandre J.; Gorelsky, Serge I.; Korobkov, Ilia; Baker, R. Tom
• Is Part Of: Chemical science. Volume 6:Issue 11(2015:Nov.)
• Page Start: 6392
• Page End: 6397
• Publication Date: 2015-08-06
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/c5sc01886b
• Languages: English
• ISSNs: 2041-6520

Abstract

Abstract : The reactivity of this T-shaped perfluoronickelacyclopentane–NHC complex with Lewis- and Brønsted acids is enhanced vs. 4-coordinate variants by its low coordination number. Abstract : A T-shaped octafluoronickelacyclopentane–NHC complex is prepared and characterized. While the solid-state structure includes a weak isopropyl-CH3 agostic interaction, the reactivity of this complex with Lewis- and Brønsted acids is clearly enhanced by its low coordination number. Reaction with Me3 SiOTf, for example, yielded a rare metal–heptafluorocyclobutyl complex whereas carboxylic acids gave substitution at the α-carbon and/or Ni–C F bond protonolysis to afford thermally robust 4 H -octafluorobutyl Ni complexes.