C-F sp2 bond functionalization mediated by niobium complexes

Michael Nechayev; Thomas L. Gianetti; Robert G. Bergman; John Arnold

doi:10.1039/c5dt02082d

C-F sp² bond functionalization mediated by niobium complexes

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

Research output: Contribution to journal › Article › peer-review

15 Scopus citations

Abstract

Insertion chemistry of isocyanide molecules was used to functionalize C-F sp² bonds after their oxidative addition across the metal center in a β-diketiminate niobium(iii) imido complex (BDI)Nb(N^tBu)(C₆H₆). The complexes formed, 3a-b ([BDI]Nb(PhC=N)(N^tBu)(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.

Original language	English (US)
Pages (from-to)	19494-19500
Number of pages	7
Journal	Dalton Transactions
Volume	44
Issue number	45
DOIs	https://doi.org/10.1039/c5dt02082d
State	Published - Jul 20 2015
Externally published	Yes

ASJC Scopus subject areas

Inorganic Chemistry

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title = "C-F sp2 bond functionalization mediated by niobium complexes",

abstract = "Insertion chemistry of isocyanide molecules was used to functionalize C-F sp2 bonds after their oxidative addition across the metal center in a β-diketiminate niobium(iii) imido complex (BDI)Nb(NtBu)(C6H6). The complexes formed, 3a-b ([BDI]Nb(PhC=N)(NtBu)(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.",

author = "Michael Nechayev and Gianetti, {Thomas L.} and Bergman, {Robert G.} and John Arnold",

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T1 - C-F sp2 bond functionalization mediated by niobium complexes

AU - Nechayev, Michael

AU - Gianetti, Thomas L.

AU - Bergman, Robert G.

AU - Arnold, John

N1 - Publisher Copyright: © The Royal Society of Chemistry.

PY - 2015/7/20

Y1 - 2015/7/20

N2 - Insertion chemistry of isocyanide molecules was used to functionalize C-F sp2 bonds after their oxidative addition across the metal center in a β-diketiminate niobium(iii) imido complex (BDI)Nb(NtBu)(C6H6). The complexes formed, 3a-b ([BDI]Nb(PhC=N)(NtBu)(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.

AB - Insertion chemistry of isocyanide molecules was used to functionalize C-F sp2 bonds after their oxidative addition across the metal center in a β-diketiminate niobium(iii) imido complex (BDI)Nb(NtBu)(C6H6). The complexes formed, 3a-b ([BDI]Nb(PhC=N)(NtBu)(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.

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JO - Dalton Transactions

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ER -

C-F sp² bond functionalization mediated by niobium complexes

Abstract

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