Mechanistic studies of the rhodium NHC catalyzed hydrodefluorination of polyfluorotoluenes

Leonid Schwartsburd; Mary F. Mahon; Rebecca C. Poulten; Mark R. Warren; Michael K. Whittlesey

doi:10.1021/om500827d

Mechanistic studies of the rhodium NHC catalyzed hydrodefluorination of polyfluorotoluenes

Leonid Schwartsburd, Mary F. Mahon, Rebecca C. Poulten, Mark R. Warren, Michael K. Whittlesey

Department of Chemistry

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Abstract

The six-membered-ring NHC complexes Rh(6-NHC)(PPh₃)₂H (6-NHC = 6-ⁱPr (1), 6-Et (2), 6-Me (3)) have been employed in the catalytic hydrodefluorination (HDF) of C₆F₅CF₃ and 2-C₆F₄HCF₃. Stoichiometric studies showed that 1 reacted with C₆F₅CF₃ at room temperature to afford cis- and trans-phosphine isomers of Rh(6-ⁱPr)(PPh₃)₂F (4), which re-form 1 upon heating with Et₃SiH. Although up to three consecutive HDF steps prove possible with C₆F₅CF₃, the ultimate effectiveness of the catalysts is limited by their propensity to undergo C-H activation of partially fluorinated toluenes to give, for example, Rh(6-ⁱPr)(PPh₃)₂(C₆F₄CF₃) (7), which was isolated and structurally characterized.

Original language	English
Pages (from-to)	6165-6170
Number of pages	6
Journal	Organometallics
Volume	33
Issue number	21
Early online date	8 Oct 2014
DOIs	https://doi.org/10.1021/om500827d
Publication status	Published - 10 Nov 2014

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10.1021/om500827d

Whittlesey revised manuscript
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Organometallics, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/om500827d
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title = "Mechanistic studies of the rhodium NHC catalyzed hydrodefluorination of polyfluorotoluenes",

abstract = "The six-membered-ring NHC complexes Rh(6-NHC)(PPh3)2H (6-NHC = 6-iPr (1), 6-Et (2), 6-Me (3)) have been employed in the catalytic hydrodefluorination (HDF) of C6F5CF3 and 2-C6F4HCF3. Stoichiometric studies showed that 1 reacted with C6F5CF3 at room temperature to afford cis- and trans-phosphine isomers of Rh(6-iPr)(PPh3)2F (4), which re-form 1 upon heating with Et3SiH. Although up to three consecutive HDF steps prove possible with C6F5CF3, the ultimate effectiveness of the catalysts is limited by their propensity to undergo C-H activation of partially fluorinated toluenes to give, for example, Rh(6-iPr)(PPh3)2(C6F4CF3) (7), which was isolated and structurally characterized.",

author = "Leonid Schwartsburd and Mahon, {Mary F.} and Poulten, {Rebecca C.} and Warren, {Mark R.} and Whittlesey, {Michael K.}",

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T1 - Mechanistic studies of the rhodium NHC catalyzed hydrodefluorination of polyfluorotoluenes

AU - Schwartsburd, Leonid

AU - Mahon, Mary F.

AU - Poulten, Rebecca C.

AU - Warren, Mark R.

AU - Whittlesey, Michael K.

PY - 2014/11/10

Y1 - 2014/11/10

N2 - The six-membered-ring NHC complexes Rh(6-NHC)(PPh3)2H (6-NHC = 6-iPr (1), 6-Et (2), 6-Me (3)) have been employed in the catalytic hydrodefluorination (HDF) of C6F5CF3 and 2-C6F4HCF3. Stoichiometric studies showed that 1 reacted with C6F5CF3 at room temperature to afford cis- and trans-phosphine isomers of Rh(6-iPr)(PPh3)2F (4), which re-form 1 upon heating with Et3SiH. Although up to three consecutive HDF steps prove possible with C6F5CF3, the ultimate effectiveness of the catalysts is limited by their propensity to undergo C-H activation of partially fluorinated toluenes to give, for example, Rh(6-iPr)(PPh3)2(C6F4CF3) (7), which was isolated and structurally characterized.

AB - The six-membered-ring NHC complexes Rh(6-NHC)(PPh3)2H (6-NHC = 6-iPr (1), 6-Et (2), 6-Me (3)) have been employed in the catalytic hydrodefluorination (HDF) of C6F5CF3 and 2-C6F4HCF3. Stoichiometric studies showed that 1 reacted with C6F5CF3 at room temperature to afford cis- and trans-phosphine isomers of Rh(6-iPr)(PPh3)2F (4), which re-form 1 upon heating with Et3SiH. Although up to three consecutive HDF steps prove possible with C6F5CF3, the ultimate effectiveness of the catalysts is limited by their propensity to undergo C-H activation of partially fluorinated toluenes to give, for example, Rh(6-iPr)(PPh3)2(C6F4CF3) (7), which was isolated and structurally characterized.

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Mechanistic studies of the rhodium NHC catalyzed hydrodefluorination of polyfluorotoluenes

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Catalytic Functionalisation of Aromatic Fluorocarbons

500 MHZ NMR SPECTROMETER TO SUPPORT ORGANIC, BIO-ORGANIC AND INORGANIC CHEMISTRY

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Mechanistic studies of the rhodium NHC catalyzed hydrodefluorination of polyfluorotoluenes

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Catalytic Functionalisation of Aromatic Fluorocarbons

500 MHZ NMR SPECTROMETER TO SUPPORT ORGANIC, BIO-ORGANIC AND INORGANIC CHEMISTRY

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