Journal of the American Chemical Society
Communication
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(12) In order to carry out the kinetic studies, the HOOH oxidant had
to be added all at once. In previous work, HOOH was introduced via
syringe pumping in order to maximize HOOH conversion into
products and minimize side reactions such as HOOH decomposition.
The conversion of HOOH decreased from 80% with syringe pumping
vs 50% under the current reaction conditions, but the stereoretention
observed in the oxidation products was identical to that obtained
under the syringe pumping conditions.
matches that of product formation, indicating a rate-limiting
step that involves decay of 2. This decay rate accelerates as a
function of water concentration and plateaus above 0.3 M,
indicating a fast pre-equilibrium binding of water onto 2
followed by rate-determining decay of the water adduct. An
H2O/D2O KIE of 2.5 is observed in the decay of 2 and in
product formation, consistent with a proton-assisted O−O
bond heterolysis of 2, a notion also supported by the Eyring
activation parameters. Taken together, these results provide the
first kinetic evidence in support of the mechanism previously
proposed for Fe(TPA)-catalyzed oxidations, involving rate-
limiting formation of an FeV(O)(OH) species from an FeIII-
OOH intermediate that is responsible for alkane and olefin
oxidations, including those with high retention of stereo-
chemistry (Scheme 1).4b,5,9a Given that several other iron
catalysts supported by tetradentate nonheme ligands have been
observed to exhibit oxidative reactivity similar to that of the
Fe(TPA)/H2O2 system, the reaction sequence proposed in
Scheme 1 is likely to serve as the mechanistic basis for this
entire family of nonheme iron catalysts.4b,9a,24
(13) Kim, C.; Chen, K.; Kim, J. H.; Que, L., Jr. J. Am. Chem. Soc.
1997, 119, 5964.
(14) Makhlynets, O. V.; Rybak-Akimova, E. V. Chem.−Eur. J. 2010,
16, 13995.
ASSOCIATED CONTENT
■
S
* Supporting Information
Table S1, decay rate of 2 as a function of olefin concentration;
Figures S1−S4, UV−vis spectroscopic data for the accumu-
lation and decay of 2 under various conditions, kinetic data for
iron-catalyzed olefin oxidation under various conditions, and
data fitting. This material is available free of charge via the
(15) Thibon, A.; Jollet, V.; Ribal, C.; Senechal-David, K.; Billon, L.;
Sorokin, A. B.; Banse, F. Chem.−Eur. J. 2012, 18, 2715.
(16) Park, M. J.; Lee, J.; Suh, Y.; Kim, J.; Nam, W. J. Am. Chem. Soc.
2006, 128, 2630.
(17) Unfortunately, these two adducts are not distinguishable by
either UV−vis or EPR methods.
(18) Whittaker, J. W.; Lipscomb, J. D. J. Biol. Chem. 1984, 259, 4476.
(19) Dunford, H. B.; Hewson, W. D.; Steiner, H. Can. J. Chem. 1978,
56, 2844.
AUTHOR INFORMATION
Corresponding Author
■
(20) (a) Traylor, T. G.; Xu, F. J. Am. Chem. Soc. 1990, 112, 178.
(b) Groves, J. T.; Watanabe, Y. J. Am. Chem. Soc. 1988, 110, 8443.
(21) (a) Lee, S. Y.; Lipscomb, J. D. Biochemistry. 1999, 38, 4423.
(b) Tinberg, C. E.; Lippard, S. J. Biochemistry. 2009, 48, 12145.
(22) (a) Kaizer, J.; Costas, M.; Que, L., Jr. Angew. Chem., Int. Ed.
2003, 42, 3671. (b) Li, F. F.; Meier, K. K.; Cranswick, M. A.;
Chakrabarti, M.; Van Heuvelen, K. M.; Munck, E.; Que, L., Jr. J. Am.
Chem. Soc. 2011, 133, 7256. (c) Liu, L. V.; Hong, S.; Cho, J.; Nam, W.;
Solomon, E. I. J. Am. Chem. Soc. 2013, 135, 3286.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work was supported by the U.S. Department of Energy
Office of Basic Energy Sciences (grant DE-FG02-03ER15455).
We thank Prof. John D. Lipscomb for valuable discussions.
(23) Yamaguchi, K.; Watanabe, Y.; Morishima, I. J. Am. Chem. Soc.
1993, 115, 4058.
(24) Company, A.; Feng, Y.; Guell, M.; Ribas, X.; Luis, J. M.; Que, L.,
Jr.; Costas, M. Chem.−Eur. J. 2009, 15, 3359.
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