Catalytic hydrodefluorination of pentafluorobenzene by [Ru(NHC)(PPh 3)2(CO)H2]: A nucleophilic attack by a metal-bound hydride ligand explains an unusual ortho-regioselectivity

Julien A. Panetier, Stuart A. Macgregor, Michael K. Whittlesey

Research output: Contribution to journalArticle

Abstract

Secret revealed: The mechanism of the catalytic hydrodefluorination of pentafluorobenzene by the N-heterocyclic carbene complex [Ru(IMes)(PPh 3)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). Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Original languageEnglish
Pages (from-to)2783-2786
Number of pages4
JournalAngewandte Chemie International Edition
Volume50
Issue number12
DOIs
Publication statusPublished - 14 Mar 2011

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Regioselectivity
Nucleophiles
Carbon Monoxide
Discrete Fourier transforms
Hydrides
Metals
Ligands
Substrates
carbene

Keywords

  • C-F activation
  • density functional calculations
  • fluoroarenes
  • hydrodefluorination
  • ruthenium

Cite this

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abstract = "Secret revealed: The mechanism of the catalytic hydrodefluorination of pentafluorobenzene by the N-heterocyclic carbene complex [Ru(IMes)(PPh 3)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). Copyright {\circledC} 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.",
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