Carbon-fluorine bond cleavage in fluoroarenes via a niobium(iii) imido complex: From stoichiometric to catalytic hydrodefluorination

Thomas L. Gianetti, Robert G. Bergman, John Arnold

Research output: Contribution to journalArticlepeer-review

58 Scopus citations

Abstract

The mechanism of activation of C-F bonds in fluoroarenes using a well-defined niobium(iii) imido complex has been investigated. The Nb(iii) arene species [BDI]Nb(NtBu)(η6-C6H6), 1, (BDI = β-diketimate), reacts stoichiometrically with fluoroarenes to yield niobium(v) aryl fluorides. Spectroscopic analysis supported by DFT calculations revealed the critical involvement of a Nb(iii) fluoroarene-bound species. In contrast to previous reports of related reactivity, we found that perfluorinated arenes (i.e. those normally assumed to bear more 'activated' C-F bonds) are, in the present system, much less reactive towards C-F bond cleavage than mono- or difluoro-substituted arenes. In addition to demonstrating stoichiometric hydrodefluorination reactions, we also describe an efficient and mild hydrodefluorination of mono- and di-fluoroarenes that is catalytic in niobium. This journal is

Original languageEnglish (US)
Pages (from-to)2517-2524
Number of pages8
JournalChemical Science
Volume5
Issue number6
DOIs
StatePublished - Jun 2014
Externally publishedYes

ASJC Scopus subject areas

  • Chemistry(all)

Fingerprint

Dive into the research topics of 'Carbon-fluorine bond cleavage in fluoroarenes via a niobium(iii) imido complex: From stoichiometric to catalytic hydrodefluorination'. Together they form a unique fingerprint.

Cite this