TY - JOUR
T1 - Catalytic hydrodefluorination of pentafluorobenzene by [Ru(NHC)(PPh 3)2(CO)H2]
T2 - A nucleophilic attack by a metal-bound hydride ligand explains an unusual ortho-regioselectivity
AU - Panetier, Julien A.
AU - Macgregor, Stuart A.
AU - Whittlesey, Michael K.
PY - 2011/3/14
Y1 - 2011/3/14
N2 - 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.
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). Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
KW - C-F activation
KW - density functional calculations
KW - fluoroarenes
KW - hydrodefluorination
KW - ruthenium
UR - http://www.scopus.com/inward/record.url?scp=79952512463&partnerID=8YFLogxK
U2 - 10.1002/anie.201006789
DO - 10.1002/anie.201006789
M3 - Article
SN - 1433-7851
VL - 50
SP - 2783
EP - 2786
JO - Angewandte Chemie International Edition
JF - Angewandte Chemie International Edition
IS - 12
ER -