Inorganic Chemistry
ARTICLE
(except PhIO) was delivered by syringe pump over 25 min to a
vigorously stirred CH3CN solution (1.1 mL) containing the iron(II)
complex and cyclohexene (if necessary, acetic acid was added before the
onset of the reaction). The solution was stirred for another 5 min after
syringe pump addition was complete. PhIO was added all at once,
followed by stirring for 30 min. The final reagent concentrations were as
follows: 2.7 ꢁ 10ꢀ3 M iron(II) complex, 0.027 M oxidant, 0.81 M
cyclohexene. The internal standard (1,4-dioxane) was added, and the
solution was subjected to GC analysis. The products were identified by
comparison of their GC retention times with those of authentic
compounds. All reactions were run at least in duplicate, the reported
yields being the average of these reactions.
(6) Nam, W. Acc. Chem. Res. 2007, 40, 522–531.
(7) Que, L., Jr. Acc. Chem. Res. 2007, 40, 493–500.
(8) Que, L., Jr.; Tolman, W. B. Nature 2008, 455, 333–340.
(9) Bruijnincx, P. C. A.; van Koten, G.; Klein Gebbink, R. J. M. Chem.
Soc. Rev. 2008, 37, 2716–2744.
(10) White, M. C.; Doyle, A. G.; Jacobsen, E. N. J. Am. Chem. Soc.
2001, 123, 7194–7195.
(11) Chen, K.; Costas, M.; Kim, J.; Tipton, A. K.; Que, L., Jr. J. Am.
Chem. Soc. 2002, 124, 3026–3035.
(12) Oldenburg, P. D.; Shteinman, A. A.; Que, L., Jr. J. Am. Chem.
Soc. 2005, 127, 15672–15673.
(13) England, J.; Britovsek, G. J. P.; Rabadia, N.; White, A. J. P. Inorg.
Chem. 2007, 46, 3752–3767.
Reaction Conditions for Catalytic Oxidations at ꢀ70 ꢀC.
For catalytic cyclohexene oxidation with H2O2 or CH3CO3H, 0.1 mL of
a 3.2 M oxidant solution cooled to ꢀ70 ꢀC was added to the vigorously
stirred solution (1.1 mL) containing iron(II) complex, cyclohexene, and
the inert internal standard (1,4-dioxane). A 1.3:1 CH2Cl2/CH3CN
mixture was used as a solvent. The final reagent concentrations were as
follows: 0.027 M iron(II) complex, 0.27 M oxidant, and 0.81 M
cyclohexene. After stirring for 1 h, 0.3 mL of a 2.5 M triphenylphosphine
solution in CH2Cl2 cooled to ꢀ70 ꢀC was added. The resulting mixture
was carefully warmed to room temperature and subjected to GC
analysis. The catalytic reactions were run in triplicate. For catalytic
cyclohexene oxidation with m-CPBA, solid m-CPBA (0.048 mmol)
cooled to ꢀ70 ꢀC was added to the vigorously stirred solution (1.2 mL)
containing the iron(II) complex, cyclohexene, and the inert internal
standard (1,4-dioxane). A 1.3:1 CH2Cl2/CH3CN mixture was used as a
solvent. The final reagent concentrations were as follows: 0.02 M
iron(II) complex, 0.04 M m-CPBA, and 0.8 M cyclohexene. After
stirring for 1 h, 0.3 mL of a 2.5 M triphenylphosphine solution in
CH2Cl2 cooled to ꢀ70 ꢀC was added. The resulting mixture was
carefully warmed to room temperature and subjected to GC analysis.
The reactions were run in triplicate. Oxidants utilized (H2O2,
CH3CO3H, and m-CPBA) do not oxidize cyclohexene at ꢀ70 ꢀC in
the absence of the iron complex.
(14) Chen, M. S.; White, M. C. Science 2007, 318, 783–787.
(15) England, J.; Davies, C. R.; Banaru, M.; White, A. J. P.; Britovsek,
G. J. P. Adv. Synth. Catal. 2008, 350, 883–897.
(16) Suzuki, K.; Oldenburg, P. D.; Que, L., Jr. Angew. Chem., Int. Ed.
2008, 47, 1887–1889.
(17) Sorokin, A. B.; Kudrik, E. V.; Bouchu, D. Chem. Commun.
2008, 2562–2564.
(18) Company, A.; Gꢀomez, L.; Fontrodona, X.; Ribas, X.; Costas, M.
Chem.—Eur. J. 2008, 14, 5727–5731.
(19) Yoon, J.; Wilson, S. A.; Jang, Y. K.; Seo, M. S.; Nehru, K.;
Hedman, B.; Hodgson, K. O.; Bill, E.; Solomon, E. I.; Nam, W. Angew.
Chem., Int. Ed. 2009, 48, 1257–1260.
(20) Schr€oder, K.; Enthaler, S.; Bitterlich, B.; Schulz, T.; Spannen-
berg, A.; Tse, M. K.; Junge, K.; Beller, M. Chem.—Eur. J. 2009, 15,
5471–5481.
(21) Gꢀomez, L.; Garcia-Bosch, I.; Company, A.; Benet-Buchholz, J.;
Polo, A.; Sala, X.; Ribas, X.; Costas, M. Angew. Chem., Int. Ed. 2009,
48, 5720–5723.
(22) Lee, S. H.; Han, J. H.; Kwak, H.; Lee, S. J.; Lee, E. Y.; Kim, H. J.;
Lee, J. H.; Bae, C.; Lee, S. N.; Kim, Y.; Kim, C. Chem.—Eur. J. 2007,
13, 9393–9398.
(23) Gelalcha, F. G.; Anilkumar, G.; Tse, M. K.; Br€uckner, A.; Beller,
M. Chem.—Eur. J. 2008, 14, 7687–7698.
(24) Chen, M. S.; White, M. C. Science 2010, 327, 566–571.
(25) M€oller, K.; Wienh€ofer, G.; Schr€oder, K.; Join, B.; Junge, K.;
Beller, M. Chem.—Eur. J. 2010, 16, 10300–10303.
(26) Das, P.; Que, L., Jr. Inorg. Chem. 2010, 49, 9479–9485.
(27) Makhlynets, O. V.; Rybak-Akimova, E. V. Chem.—Eur. J. 2010,
16, 13995–14006.
(28) Mas-Ballestꢀe, R.; Que, L., Jr. J. Am. Chem. Soc. 2007, 129,
15964–15972.
(29) Kim, C.; Chen, K.; Kim, J.; Que, L., Jr. J. Am. Chem. Soc. 1997,
119, 5964–5965.
’ ASSOCIATED CONTENT
Supporting Information. 1H NMR chemical shifts for
S
b
oxoiron(IV) complex 1d, simulated and experimental EPR
spectra of species 2c, and EPR monitoring of the interaction of
complex 2 with m-CPBA. This material is available free of charge
(30) 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, 3665–3670.
(31) Lobanova, M. V.; Bryliakov, K. P.; Duban, E. A.; Talsi, E. P.
Mendeleev Commun. 2003, 175–177.
(32) Duban, E. A.; Bryliakov, K. P.; Talsi, E. P. Mendeleev Commun.
2005, 12–14.
(33) Duban, E. A.; Bryliakov, K. P.; Talsi, E. P. Eur. J. Inorg. Chem.
2007, 852–857.
(34) Park, M. J.; Lee, J.; Suh, Y.; Kim, J.; Nam, W. J. Am. Chem. Soc.
2006, 128, 2630–2634.
’ AUTHOR INFORMATION
Corresponding Author
*Fax: þ7 383 3308056. E-mail: talsi@catalysis.ru.
’ ACKNOWLEDGMENT
The authors thank the Russian Foundation for Basic Research,
Grant 09-03-00087, for financial support.
(35) de Oliveira, F. T.; Chanda, A.; Banerjee, D.; Shan, X.; Mondal,
S.; Que, L., Jr.; Bominaar, E. L.; M€unck, E.; Collins, T. J. Science 2007,
315, 835–838.
(36) Lyakin, O. Y.; Bryliakov, K. P.; Britovsek, G. J. P.; Talsi, E. P.
J. Am. Chem. Soc. 2009, 131, 10798–10799.
’ REFERENCES
(1) Solomon, E. I.; Brunold, T. C.; Davis, M. I.; Kemsley, J. N.; Lee,
S.-K.; Lehnert, N.; Neese, F.; Skulan, A. J.; Yang, Y.-S.; Zhou, J. Chem.
Rev. 2000, 100, 235–349.
(37) Some results described in this paper were partially presented in
our short communication (see ref 36).
(2) Costas, M.; Mehn, M. P.; Jensen, M. P.; Que, L., Jr. Chem. Rev.
2004, 104, 939–986.
(3) Tshuva, E. Y.; Lippard, S. J. Chem. Rev. 2004, 104, 987–1012.
(4) Kryatov, S. V.; Rybak-Akimova, E. V.; Schindler, S. Chem. Rev.
2005, 105, 2175–2226.
(38) Seo, M. S.; Kamachi, T.; Kouno, T.; Murata, K.; Park, M. J.;
Yoshizawa, K.; Nam, W. Angew. Chem., Int. Ed. 2007, 46, 2291–2294.
(39) Duelund, L.; Hazell, R.; McKenzie, C. J.; Nielsen, L. P.;
Toftlund, H. J. Chem. Soc., Dalton Trans. 2001, 152–156.
(5) Oldenburg, P. D.; Que, L., Jr. Catal. Today 2006, 117, 15–21.
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