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 language | English (US) |
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Pages (from-to) | 2517-2524 |
Number of pages | 8 |
Journal | Chemical Science |
Volume | 5 |
Issue number | 6 |
DOIs | |
State | Published - Jun 2014 |
Externally published | Yes |
ASJC Scopus subject areas
- Chemistry(all)