Catalytic Hydrodefluorination of Pentafluorobenzene by [Ru(NHC)(PPh₃)₂(CO)H₂]: A Nucleophilic Attack by a Metal-Bound Hydride Ligand Explains an Unusual ortho-Regioselectivity

Secret revealed: The mechanism of the catalytic hydrodefluorination of pentafluorobenzene by the N‐heterocyclic carbene complex [Ru(IMes)(PPh3)2(CO)H2] has been investigated by DFT calculations. Two sets of novel pathways (concerted and stepwise) have been defined whereby a Ru H ligand can act as a...

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Veröffentlicht in:Angewandte Chemie (International ed.) 2011-03, Vol.50 (12), p.2783-2786
Hauptverfasser: Panetier, Julien A, Macgregor, Stuart A, Whittlesey, Michael K
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Sprache:eng
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Zusammenfassung:Secret revealed: The mechanism of the catalytic hydrodefluorination of pentafluorobenzene by the N‐heterocyclic carbene complex [Ru(IMes)(PPh3)2(CO)H2] has been investigated by DFT calculations. Two sets of novel pathways (concerted and stepwise) have been defined whereby a Ru H ligand can act as a nucleophile at the fluoroarene substrate. The most accessible pathway equates to the formation of 1,2,3,4‐C6F4H2 and thus accounts for the unusual regioselectivity that is observed experimentally (see scheme).
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201006789