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

doi:10.1002/anie.201006789

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

School of Chemistry

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

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).

Original language	English
Pages (from-to)	2783-2786
Number of pages	4
Journal	Angewandte Chemie - International Edition
Volume	50
Issue number	12
DOIs	https://doi.org/10.1002/anie.201006789
Publication status	Published - 14 Mar 2011

Keywords

C-F activation
density functional calculations
fluoroarenes
hydrodefluorination
ruthenium

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Cite this

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title = "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",

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).",

keywords = "C-F activation, density functional calculations, fluoroarenes, hydrodefluorination, ruthenium",

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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. / Panetier, Julien A.; MacGregor, Stuart A.; Whittlesey, Michael K.
In: Angewandte Chemie - International Edition, Vol. 50, No. 12, 14.03.2011, p. 2783-2786.

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

TY - JOUR

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T2 - A nucleophilic attack by a metal-bound hydride ligand explains an unusual ortho-regioselectivity

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AU - MacGregor, Stuart A.

AU - Whittlesey, Michael K.

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AB - 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).

KW - C-F activation

KW - density functional calculations

KW - fluoroarenes

KW - hydrodefluorination

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