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COMMUNICATION
complex (Figure S14), indicating that the oxidation of sulfides
by 2 occurs via a two-electron oxidation process. In other oxida-
tion reactions, such as in the oxidation of olefins, alcohols, and
aromatic compounds, we observed the formation of 3 via one-
electron oxidation process (data not shown). Although we have
reported preliminary results that non-heme Mn(IV)ꢀoxo complex 2
is a versatile oxidant in the oxidation of a variety of substrates via one-
versus two-electron oxidation processes, detailed studies are under-
way to elucidate the mechanisms of the oxidation of the substrates by
mononuclear non-heme manganese(IV)ꢀoxo complexes.
(6) Manganeseꢀoxo porphyrins: (a) Groves, J. T.; Lee, J.; Marla,
S. S. J. Am. Chem. Soc. 1997, 119, 6269. (b) Jin, N.; Ibrahim, M.; Spiro,
T. G.; Groves, J. T. J. Am. Chem. Soc. 2007, 129, 12416. (c) Song, W. J.;
Seo, M. S.; George, S. D.; Ohta, T.; Song, R.; Kang, M.-J.; Tosha, T.;
Kitagawa, T.; Solomon, E. I.; Nam, W. J. Am. Chem. Soc. 2007, 129, 1268.
(d) Lee, J. Y.; Lee, Y.-M.; Kotani, H.; Nam, W.; Fukuzumi, S. Chem.
Commun. 2009, 704.
(7) Non-heme manganeseꢀoxo complexes: (a) Parsell, T. H.; Behan,
R. K.; Green, M. T.; Hendrich, M. P.; Borovik, A. S. J. Am. Chem. Soc. 2006,
128, 8728. (b) Yin, G.; Danby, A. M.; Kitko, D.; Carter, J. D.; Scheper,
W. M.; Busch, D. H. J. Am. Chem. Soc. 2007, 129, 1512.
(c) Yin, G.; Danby, A. M.; Kitko, D.; Carter, J. D.; Scheper, W. M.; Busch,
D. H. J. Am. Chem. Soc. 2008, 130, 16245. (d) Parsell, T. H.; Yang, M.-Y.;
Borovik, A. S. J. Am. Chem. Soc. 2009, 131, 2762. (e)Kurahashi, T.; Kikuchi,
A.; Shiro, Y.; Hada, M.; Fujii, H. Inorg. Chem. 2010, 49, 6664. (f) Sawant,
S. C.; Wu, X.; Cho, J.; Cho, K.-B.; Kim, S. H.; Seo, M. S.; Lee, Y.-M.; Kubo,
M.; Ogura,T.; Shaik,S.;Nam,W. Angew. Chem., Int.Ed.2010, 49, 8190. (g)
Garcia-Bosch, I.; Company, A.; Cady, C. W.; Styring, S.; Browne, W. R.;
Ribas, X.; Costas, M. Angew. Chem., Int. Ed. 2011, 50, 5648.
’ ASSOCIATED CONTENT
S
Supporting Information. Experimental and DFT details,
b
Tables S1ꢀS7, and Figures S1ꢀS14. This material is available
(8) Corrole and corrolazine manganeseꢀoxo complexes: (a) Prokop,
K. A.;deVisser, S. P.; Goldberg, D. P. Angew. Chem., Int. Ed. 2010, 49, 5091.
(b) Han, Y.; Lee, Y.-M.; Mariappan, M.; Fukuzumi, S.; Nam, W. Chem.
Commun. 2010, 46, 8160. (c) Kumar, A.; Goldberg, I.; Botoshansky, M.;
Buchman, Y.; Gross, Z. J. Am. Chem. Soc. 2010, 132, 15233. (d) Fukuzumi,
S.; Kotani, H.; Prokop, K. A.; Goldberg, D. P. J. Am. Chem. Soc. 2011,
133, 1859.
(9) (a) Kaizer, J.; Klinker, E. J.; Oh, N. Y.; Rohde, J.-U.; Song, W. J.;
Stubna, A.; Kim, J.; M€unck, E.; Nam, W.; Que, L., Jr. J. Am. Chem. Soc.
2004, 126, 472. (b) Seo, M. S.; Kim, N, H.; Cho, K.-B.; So, J. E.; Park,
S. K.; Clꢀemancey, M.; Garcia-Serres, R.; Latour, J.-M.; Shaik, S.; Nam, W.
Chem. Sci 2011, 2, 1039.
(10) (a) Groves, J. T.; McClusky, G. A. J. Am. Chem. Soc. 1976,
98, 859. (b) Ortiz de Montellano, P. R.; Stearns, R. A. J. Am. Chem. Soc.
1987, 109, 3415. (c) Sch€oneboom, J. C.; Cohen, S.; Lin, H.; Shaik, S.;
Thiel, W. J. Am. Chem. Soc. 2004, 126, 4017. (d) Hirao, H.; Kumar, D.;
Que, L., Jr.; Shaik, S. J. Am. Chem. Soc. 2006, 128, 8590.
’ AUTHOR INFORMATION
Corresponding Author
ypushkar@purdue.edu; wwnam@ewha.ac.kr
’ ACKNOWLEDGMENT
The research at EWU was supported by GRL (2010-00353)
and WCU (R31-2008-000-10010-0). The research at Purdue was
supported by the Department of Energy, Office of Basic Energy
Sciences (DOE-BES) (DE-FG02-10ER16184 to Y.P.) and an
NSF Graduate Research Fellowship under Grant 0833366
(K.M.D.). Synchrotron facilities were provided by the Advanced
Photon Source (APS) at Argonne National Laboratory, operated
by DOE-BES under Contract No. DE-AC02-06CH11357. We
thank Dr. Steve Heald and Dr. Dale Brewer for help with
experiments at Beamline BM-20, APS.
(11) Evans, D. F. J. Chem. Soc. 1959, 2003.
(12) (a) Ayougou, K.; Bill, E.; Charnock, J. M.; Garner, C. D.;
Mandon, D.; Trautwein, A. X.; Weiss, R.; Winkler, H. Angew. Chem., Int.
Ed. Engl. 1995, 34, 343. (b) Kurahashi, T.; Kikuchi, A.; Tosha, T.; Shiro,
Y.; Kitagawa, T.; Fujii, H. Inorg. Chem. 2008, 47, 1674.
’ REFERENCES
(13) (a) Bortolini, O.; Meunier, B.; Friant, P.; Ascone, I.; Goulon, J.
New J. Chem. 1986, 10, 39. (b) Lassalle-Kaiser, B.; Hureau, C.; Pantazis,
D. A.; Pushkar, Y.; Guillot, R.; Yachandra, V. K.; Yano, J.; Neese, F.;
Anxolabꢀehꢁere-Mallart, E. Energy Environ. Sci. 2010, 3, 924.
(1) (a) Ortiz de Montellano, P. R. Cytochrome P450: Structure,
Mechanism, and Biochemistry, 3rd ed.; Kluwer: New York, 2005. (b)
Abu-Omar, M. M.; Loaiza, A.; Hontzeas, N. Chem. Rev. 2005, 105, 2227.
(c) Krebs, C.; Fujimori, D. G.; Walsh, C. T.; Bollinger, J. M., Jr. Acc.
Chem. Res. 2007, 40, 484. (d) Green, M. T. Curr. Opin. Chem. Biol. 2009,
13, 84. (e) Ortiz de Montellano, P. R. Chem. Rev. 2010, 110, 932. (f)
Shaik, S.; Lai, W.; Chen, H.; Wang, Y. Acc. Chem. Res. 2010, 43, 1154.
(2) (a) Mayer, J. M. Acc. Chem. Res. 2011, 44, 36. (b) Borovik, A. S.
Chem. Soc. Rev. 2011, 40, 1870. (c) Gunay, A.; Theopold, K. H. Chem.
Rev. 2010, 110, 1060. (d) Warren, J. J.; Tronic, T. A.; Mayer, J. M. Chem.
Rev. 2010, 110, 6961. (e) Stone, K. L.; Borovik, A. S. Curr. Opin. Chem.
Biol. 2009, 13, 114.
(3) (a) Abu-Omar, M. M. Dalton Trans. 2011, 40, 3435. (b)
Bruijnincx, P. C. A.; van Koten, G.; Klein Gebbink, R. J. M. Chem. Soc.
Rev. 2008, 37, 2716. (c) van Eldik, R. Coord. Chem. Rev. 2007, 251, 1649.
(d) Groves, J. T. J. Inorg. Biochem. 2006, 100, 434.
(4) (a) Meunier, B.; Robert, A.; Pratviel, G.; Bernadou, J. In The
Porphyrin Handbook; Kadish, K. M., Smith, K. M., Guilard, R., Eds.;
Academic Press: San Diego, 2000; Vol. 4, Chapter 31, pp 119ꢀ187. (b)
Murphy, A.; Dubois, G.; Stack, T. D. P. J. Am. Chem. Soc. 2003,
125, 5250. (c) Nehru, K.; Kim, S. J.; Kim, I. Y.; Seo, M. S.; Kim, Y.;
Kim, S.-J.; Kim, J.; Nam, W. Chem. Commun. 2007, 4623. (d) Terry, T. J.;
Stack, T. D. P. J. Am. Chem. Soc. 2008, 130, 4945.
(14) Hull, J. F.; Balcells, D.; Sauer, E. L. O.; Raynaud, C.; Brudvig,
G. W.; Crabtree, R. H.; Eisenstein, O. J. Am. Chem. Soc. 2010, 132, 7605.
(15) The product distribution and yields were different when the
reaction was carried out in the presence of O2. Similarly, the source of
oxygen in the oxygenated products was molecular oxygen in this reaction,
not the Mn(IV)ꢀoxo complex (see Figure S7 for a detailed discussion).
(16) Preliminary DFT calculations suggested that there is a signifi-
cant activation barrier for the rebound of the hydroxyl group to the alkyl
radical (Scheme 1, step b), which would constitute a rate-limiting step if
the reaction indeed were to proceed by this route.
(17) (a) Lim, M. H.; Rohde, J.-U.; Stubna, A.; Bukowski, M. R.;
Costas, M.; Ho, R. Y. N.; M€unck, E.; Nam, W.; Que, L., Jr. Proc. Natl.
Acad. Sci. U.S.A. 2003, 100, 3665. (b) Oh, N. Y.; Suh, Y.; Park, M. J.; Seo,
M. S.; Kim, J.; Nam, W. Angew. Chem., Int. Ed. 2005, 44, 4235. (c) Park,
M. J.; Lee, J.; Suh, Y.; Kim, J.; Nam, W. J. Am. Chem. Soc. 2006, 128, 2630.
(d) Nehru, K.; Seo, M. S.; Kim, J.; Nam, W. Inorg. Chem. 2007, 46, 293.
(e) de Visser, S. P.; Oh, K.; Han, A.-R.; Nam, W. Inorg. Chem. 2007,
46, 4632.
(5) (a) McEvoy, J. P.; Brudvig, G. W. Chem. Rev. 2006, 106, 4455. (b)
Meyer, T. J.; Huynh, M. H. V.; Thorp, H. H. Angew. Chem., Int. Ed. 2007,
46, 5284. (c) Pecoraro, V. L.; Hsieh, W.-Y. Inorg. Chem. 2008, 47, 1765.
(d) Romain, S.; Vigara, L.; Llobet, A. Acc. Chem. Res. 2009, 42, 1944.
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dx.doi.org/10.1021/ja208523u |J. Am. Chem. Soc. 2011, 133, 20088–20091