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A T-shaped Ni[?2-(CF2)4-] NHC complex: unusual Csp3 -F and M-CF bond functionalization reactions.

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 Me3SiOTf, for example, yielded a rare metal-heptafluorocyclobutyl complex whereas carboxylic acids gave substitution at the ?-carbon and/or Ni-CF bond protonolysis to afford thermally robust 4H-octafluorobutyl Ni complexes.

SUBMITTER: Andrella NO

PROVIDER: S-EPMC6054117 | biostudies-literature | 2015 Nov

REPOSITORIES: biostudies-literature

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A T-shaped Ni[κ2-(CF2)4-] NHC complex: unusual Csp3 -F and M-CF bond functionalization reactions.

Andrella Nicholas O NO Sicard Alexandre J AJ Gorelsky Serge I SI Korobkov Ilia I Baker R Tom RT

Chemical science 20150806 11

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 Me3SiOTf, for example, yielded a rare metal-heptafluorocyclobutyl complex whereas carboxylic acids gave substitution at the α-carbon and/or Ni-CF bond protonolysis to affor ...[more]

PMID: 30090259

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