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ChemComm
DOI: 10.1039/C7CC00933J
COMMUNICATION
Journal Name
4
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5
6
Scheme 2 Proposed mechanism for the formation of
2 by reaction of
2
1
000, 2, 1541. (b) J. E. Lyons, P. E. Ellis, H. K. Myers, J. Catal.,
995, 155, 59. C.-M. Che, V. K.-Y. Lo, C.-Y. Zhou and J.-S.
2
complex 1 and O .
Unlike previous reports with iron-heme and Fe-TAML
complexes, this iron(IV) dimer has limited stability in
presence of substrate like alkene or alkanes, since it rests in an
Huang, Chem. Soc. Rev., 2011, 40, 1950.
2
(a) Y.-M. Lee, S. Hong, Y. Morimoto, W. Shin, S. Fukuzumi
and W. Nam, J. Am. Chem. Soc., 2010, 132, 10668. (b) Y. He
and C. R. Goldsmith, Chem. Commun., 2012, 48, 10532. (c) D.
V
III
equilibrium with the Fe (O) and Fe complex. Kinetic evidence
for epoxidation reaction indicates presence of such an
Sheet and T. K. Paine, Chem. Sci., 2016, 7, 5322. (d) S. Sahu
and D. P. Goldberg, J. Am. Chem. Soc., 2016, 138, 11410.
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W. A. Gunderson, A. C. Weitz, M. P. Hendrich, A. D. Ryabov
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105, 181. (b) M. W. Grinstaff, M. G. Hill, J. A. Labinger and H.
B. Gray, Science, 1994, 264, 1311.
1
3(d)
equilibrium.
In addition, when this dimer was incubated
7
8
III
with a nitro substituted [(NO -bTAML)Fe (Cl)] complex, the
2-
16
2
scrambling of O-atom from
2 was observed by high-resolution
†
mass spectrometry (HR-MS) analysis (Fig. S11, ESI ) which
substantiates our hypothesis. Upon addition of alkene, the
V
Fe (O) reacts with alkene to form epoxide and regenerates the
III
starting Fe complex, which again reacts with another O2
9
1
S. O. Kim, C. V. Sastri, M. S. Seo, J. Kim and W. Nam, J. Am.
Chem. Soc., 2005, 127, 4178.
molecule to start the cycle once again. This catalytic cycle
continues until the catalyst precipitates out from the solution.
0 J. T. Groves and Y. Watanabe, J. Am. Chem. Soc., 1986, 108
834.
both the O-atoms of O molecule are utilized for substrate 11 (a) R. A. Leising and K. J. Takeuchi, Inorg. Chem., 1987, 26
,
We believe that complex
1 functions like a dioxygenase, where
7
2
,
oxidation. Such atom-economical use of O is clearly superior
2
4391. (b) A. S. Goldstein, R. H. Beer and R. S. Drago, J. Am.
Chem. Soc., 1994, 116, 2424. (c) R. Neumann and M. Dahan,
Nature, 1997, 388, 353.
to monooxygenases where one O-atom inserts into the organic
substrate while the other O-atom is reduced to H O in the
2
1
2 (a) M. Momenteau and C. A. Reed, Chem. Rev., 1994, 94
6
,
59. (b) N. Kitajima, N. Tamura, H. Amagai, H. Fukui, Y. Moro-
presence of coreductant.
III
In summary, monomeric Fe -bTAML complex
1
is
oka, Y. Mizutani, T. Kitagawa, R. Mathur, K. Heerwegh, C. A.
Reed, C. R. Randall, L. Que, Jr. and K. Tatsumi, J. Am. Chem.
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Angew. Chem. Int. Ed. 2008, 47, 7064. (f) W. Nam, Acc.
Chem. Res., 2015, 48, 2415. (g) S. Chatterjee and T. K. Paine,
Angew. Chem. Int. Ed., 2015, 54, 9338.
competent to activate molecular dioxygen (O ) to generate a
2
dimeric complex
2 which is reactive towards alkenes. The
catalytic use of O2 by a monomeric iron-complex towards
epoxidation reaction without the use of any coreductant is
unprecedented. Above investigations indicate the involvement
V
of a high valent Fe (O) species during the reaction of complex
1
and O with alkene; although we are currently unable to
2
spectroscopically observe this intermediate under the reaction
conditions. Further investigations for understanding the
binding of O with monomeric iron(III) centre and sequential 13 (a) C. Panda, M. Ghosh, T. Panda, R. Banerjee and S. Sen
2
steps for the dimer formation are being carried out in our
laboratory.
Gupta, Chem. Commun., 2011, 47, 8016. (b) M. Ghosh, K. K.
Singh, C. Panda, A. Weitz, M. P. Hendrich, T. J. Collins, B. B.
Dhar and S. Sen Gupta, J. Am. Chem. Soc., 2014, 136, 9524.
S. S. G. acknowledges SERB, New Delhi (Grant no
EMR/2014/00016) and IISER-Kolkata (“Start-up Grant”) for funding.
K. K. S. acknowledge UGC-New Delhi for fellowship. SSG thanks Dr
Soumen Mukherjee for helpful discussion regarding oxygen
activation in dichloromethane.
(
c) K. K. Singh, M. k. Tiwari, M Ghosh, C. Panda, A. Weitz, M.
P. Hendrich, B. B. Dhar, K. Vanka, and S. Sen Gupta, Inorg.
Chem., 2015, 54, 1535. (d) K. K. Singh, M. k. Tiwari, B. B.
Dhar, K. Vanka and S. Sen Gupta, Inorg. Chem., 2015, 54
6112.
,
1
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1
Elgren, H. G. Jang, L. L. Pearce and L. Que, Jr., J. Am. Chem.
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and M. Newcomb, Org. Lett., 2009, 11, 2089.
Notes and references
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(a) K. A. Jørgensen, Chem. Rev., 1989, 89, 431. (b) B. S. Lane
and K. Burgess, Chem. Rev., 2003, 103, 2457.
2
(a) M. Costas, M. P. Mehn, M. P. Jensen and L. Que, Jr.,
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Nature, 2008, 455, 333. (c) B. Meunier, S. P. de Visser and S. 15 M. S. Seo, J.-H. In, S. O. Kim, N. Y. Oh, J. Hong, J. Kim, L. Que,
Shaik, Chem. Rev., 2004, 104, 3947.
Jr. and W. Nam, Angew. Chem. Int. Ed., 2004, 43, 2417.
(a) J. T. Groves, T. E. Nemo and R. S. Myers, J. Am. Chem. 16 For synthesis of [(NO -bTAML)Fe (Cl)] see C. Panda, J.
III
-
3
2
Soc., 1979, 101, 1032. (b) R. Mas-Balleste and L. Que, Jr., J.
Am. Chem. Soc., 2007, 129, 15964. (c) F. T. de Oliveira, A.
Chanda, D. Banerjee, X. Shan, S. Mondal, L. Que, Jr., E. L.
Bominaar, E. Münck and T. J. Collins, Science, 2007, 315, 835.
Debgupta, D. Diaz Diaz, K. K. Singh, S. Sen Gupta and B. B.
Dhar, J. Am. Chem. Soc., 2014, 136, 12273.
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| J. Name., 2012, 00, 1-3
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