Unravelling nucleophilic aromatic substitution pathways with bimetallic nucleophiles

The reaction of a metal complex containing a polar Fe-Mg bond with 2-(pentafluorophenyl)pyridine leads to selective C-F bond activation. A stepwise S N Ar mechanism involving attack of the bimetallic nucleophile on the electron-deficient aromatic ring has been identified by DFT calculations. Despite...

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Bibliographic Details
Published in:Chemical communications (Cambridge, England) England), 2019-02, Vol.55 (12), p.185-188
Main Authors: Garçon, Martí, Bakewell, Clare, White, Andrew J. P, Crimmin, Mark R
Format: Article
Language:English
Subjects:
Bimetals
Coordination compounds
Crystallography
Iron
Nucleophiles
Substitution reactions
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Summary:The reaction of a metal complex containing a polar Fe-Mg bond with 2-(pentafluorophenyl)pyridine leads to selective C-F bond activation. A stepwise S N Ar mechanism involving attack of the bimetallic nucleophile on the electron-deficient aromatic ring has been identified by DFT calculations. Despite the long and rich history of metal anions in organic synthesis, this is the first time the S N Ar mechanism has been elucidated in detail for metal-based nucleophiles. Reaction of nucleophiles containing polar (Fe-Mg) and apolar (Mg-Mg) bonds with 2-(pentafluorophenyl)pyridine are calculated to proceed by stepwise and concerted S N Ar pathways respectively.
ISSN:1359-7345
1364-548X
DOI:10.1039/c8cc09701a