C-F sp super(2) bond functionalization mediated by niobium complexes

Insertion chemistry of isocyanide molecules was used to functionalize C-F sp super(2) bonds after their oxidative addition across the metal center in a beta -diketiminate niobium(iii) imido complex (BDI)Nb(N super()tu)(C sub(6)H sub(6)). The complexes formed, 3a-b ([BDI]Nb(PhC&z.dbd; N)(N super(...

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Bibliographic Details
Published in:Dalton transactions : an international journal of inorganic chemistry 2015-11, Vol.44 (45), p.19494-19500
Main Authors: Nechayev, Michael, Gianetti, Thomas L, Bergman, Robert G, Arnold, John
Format: Article
Language:English
Subjects:
Aromatic compounds
Bonding
Exchange
Hydrides
Insertion
Niobium
NMR spectroscopy
X-rays
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Summary:Insertion chemistry of isocyanide molecules was used to functionalize C-F sp super(2) bonds after their oxidative addition across the metal center in a beta -diketiminate niobium(iii) imido complex (BDI)Nb(N super()tu)(C sub(6)H sub(6)). The complexes formed, 3a-b ([BDI]Nb(PhC&z.dbd; N)(N super()tu)(F) (R = 1,6-diisopropylphenyl, tert-butyl), were characterized by NMR spectroscopy and X-ray analysis. Further treatment with phenylsilane induced H/F exchange under mild conditions, which was followed by hydride transfer to the inserted isocyanide. Divergent reactivity was observed when the two analogous aryl and tert-butyl isocyanide insertion products were treated with phenylsilane.
ISSN:1477-9226
1477-9234
DOI:10.1039/c5dt02082d