ACS Catalysis
X-ray crystallographic data for 3 (CIF)
Research Article
(7) Johnson, S. A.; Huff, C. W.; Mustafa, F.; Saliba, M. J. Am. Chem.
Soc. 2008, 130, 17278−17279.
(8) Reade, S. P.; Mahon, M. F.; Whittlesey, M. K. J. Am. Chem. Soc.
2009, 131, 1847−1861.
NMR spectra for 3, phosphine exchange experiments for
1 and 2, computed structures and energies for all
computational results (PDF)
(9) For other ortho-selective systems of simple fluoroaromatics
without directing groups, see: (a) Chen, Z.; He, C. Y.; Yin, Z. S.;
Chen, L. Y.; He, Y.; Zhang, X. G. Angew. Chem., Int. Ed. 2013, 52,
5813−5817. (b) He, Y.; Chen, Z.; He, C. Y.; Zhang, X. G. Chin. J.
Chem. 2013, 31, 873−877. (c) Podolan, G.; Lentz, D.; Reissig, H.-U.
Angew. Chem., Int. Ed. 2013, 52, 9491−9494.
AUTHOR INFORMATION
Corresponding Authors
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(10) Panetier, J. A.; Macgregor, S. A.; Whittlesey, M. K. Angew.
Chem., Int. Ed. 2011, 50, 2783−2786.
Notes
(11) Macgregor, S. A.; McKay, D.; Panetier, J. A.; Whittlesey, M. K.
Dalton Trans. 2013, 42, 7386−7395.
The authors declare no competing financial interest.
(12) NHC abbreviations: IPr = 1,3-bis-(2,6-diisopropylphenyl)
imidazol-2-ylidene; IMes = 1,3-bis-(2,4,6-trimethylphenyl)imidazol-2-
ylidene.
ACKNOWLEDGMENTS
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We acknowledge financial support from the EPSRC through
grant numbers EP/J010677/1 (D.M.) and EP/J009962/1
(I.M.R.). We thank Dr Tim Woodman for help with NMR
experiments and Johnson Matthey PLC for the loan of
hydrated RuCl3.
(13) For a review of computational work on C-F activation see :
Algarra, A. G.; Macgregor, S. A.; Panetier, J. A. Mechanistic Studies of
C-X Bond Activation at Transition-Metal Centers. In Comprehensive
Inorganic Chemistry II, Reedijk, J., Poeppelmeier, E., Eds.; Elsevier:
Oxford, 2013; Vol. 9, pp 635−694.
(14) Reade, S. P.; Acton, A. L.; Mahon, M. F.; Martin, T. A.;
Whittlesey, M. K. Eur. J. Inorg. Chem. 2009, 1774−1785.
(15) Free energies for PPh3/C5F5N exchange at 1 and 2 were
computed to be +20.0 kcal/mol and +15.6 kcal/mol respectively at the
BP86-D3(THF) level, but as reported by others,15 these values show a
significant functional dependence (see Table S2, Supporting
Information). The precise free energy change for this pre-equilibrium
will affect the overall barrier for HDF, although here we have focussed
on the regioselectivity of the subsequent HDF process. (a) Minenkov,
Y.; Occhipinti, G.; Jensen, V. R. J. Phys. Chem. A 2009, 113, 11833−
11844.
(16) In comparison, the free energies for binding Et3SiH or a THF
solvent molecule at A are 8.0 and 0.3 kcal/mol, respectively.
(17) Hatnean, J. A.; Johnson, S. A. Organometallics 2012, 31, 1361−
1373.
(18) (a) Nova, A.; Erhardt, S.; Jasim, N. A.; Perutz, R. N.; Macgregor,
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S. A.; McGrady, J. E. Organometallics 2010, 29, 1824−1831.
(19) Huhmann-Vincent, J.; Scott, B. L.; Kubas, G. J. Inorg. Chem.
1998, 38, 115−124.
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