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COMMUNICATION
DOI: 10.1039/C4CC09967B
1
the reaction of [(tpa)MnII]2+ with iodobenzene diacetate and
stabilized inside AlꢀMCMꢀ41.
The rate of formation of phenol in the hydroxylation of
benzene with H2O2 catalysed by [(tpa)MnII]2+@AlꢀMCMꢀ41
was proportional to concentrations of [(tpa)MnII]2+@AlꢀMCMꢀ
41 and benzene, but independent of concentration of H2O2
(Figs. S9, S10 and S11†) as given by eqn 1,
derivatives (Figs. S4ꢀS6, S9a, S10 and S11), H NMR (Fig S7), EPR
spectra (Fig. S8) and phenol formation rate (Fig. S9b). See
DOI: 10.1039/c000000x/
1
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2
3
d[PhOH]/d
t
=
kcat[cat][benzene]
(1)
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where kcat is the catalytic rate constant and [cat] is an Mn
concentration in [(tpa)MnII]2+@AlꢀMCMꢀ41. Formation rates
of phenol increased linearly with increasing concentration of
[(tpa)MnII]2+ in the presence of large excess of benzene (Fig.
S9a†). The secondꢀorder rate constant (kcat) was determined to
be 6.5 Mꢀ1 hꢀ1 from the slope of a linear plot of the formation
rates of phenol vs. concentrations of [(tpa)MnII]2+ (Fig. S9b†).
The kinetic formulation in eqn 1 suggests that the rateꢀ
determining step in the catalytic hydroxylation of benzene with
H2O2 may be the hydroxylation of benzene by
[(tpa)MnIV(O)]2+@AlꢀMCMꢀ41, which is produced by the
reaction of [(tpa)MnII]2+ with H2O2 inside AlꢀMCMꢀ41 as
shown in Scheme 1.
6
7
8
J. Chen, X. Wu, K. M. Davis, Y.ꢀM. Lee, M. S. Seo, K.ꢀB. Cho, H.
Yoon, Y. J. Park, S. Fukuzumi, Y. N. Pushkar and W. Nam, J. Am.
Chem. Soc., 2013, 135, 6388.
9
H. Yoon, Y. Morimoto, K. Ohkubo, Y.ꢀM. Lee, W. Nam and S.
Fukuzumi, Chem. Commun., 2012, 48, 11187.
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11
H. Yoon, Y.ꢀM. Lee, X. Wu, K.ꢀB. Cho, Y. N. Pushkar, W. Nam and
S. Fukuzumi, J. Am. Chem. Soc., 2013, 135, 9186.
A manganese(VII) nitrido oxo species has recently been reported to
be able to oxidize alkanes; see: L. Ma, Y. Pan, W.ꢀL. Man, H.ꢀK.
Kwong, W. W. Y. Lam, G. Chen, K.ꢀC. Lau and T.ꢀC. Lau, J. Am.
Chem. Soc., 2014, 136, 7680.
12
13
A. R. Oki, J. Glerup and D. J. Hodgson, Inorg. Chem., 1990, 29,
2435.
Scheme 1 Catalytic cycle in hydroxylation of benzene with H2O2 catalysed by
[(tpa)MnII]2+ incorporated in Al-MCM-41.
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In conclusion, selective hydroxylation of benzene
derivatives and alkanes with H2O2 was efficiently catalysed by
[(tpa)MnII]2+ incorporated in AlꢀMCMꢀ41 to yield the
corresponding phenol and alcohol derivatives without further
oxidation resulted from the highly acidic nature of silicaꢀ
alumina surfaces at ambient temperature. The MnIV(O) species
([(tpa)MnIV(O)]2+), which is responsible for the hydroxylation
of benzene derivatives and alkanes, is produced by the reaction
of [(tpa)MnII]2+ with H2O2 inside AlꢀMCMꢀ41 and thus
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15
16
17
18
stabilized without formation of [(tpa)2Mn2(µ
ꢀO)2]3+. The
strategy to use AlꢀMCMꢀ41 for stabilizing a reactive species,
which would otherwise be converted to the much less reactive
species, reported in this study provides a convenient way to
develop efficient oxidation catalysts.
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Small amount of mꢀ and pꢀnitorophenol was formed at prolonged
reaction time.
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Notes and references
Department of Material and Life Science, Graduate School of
Engineering, ALCA, Japan Science and Technology Agency (JST), Osaka
University,
fukuzumi@chem.eng.osakaꢀu.ac.jp; Fax: +81ꢀ6ꢀ6879ꢀ7370
Electronic Supplementary Information (ESI) available: Experimental
Suita,
Osaka
565ꢀ0871,
Japan;
Eꢀmail:
†
details and N2ꢀadsorption desorption isotherm (Fig. S1), powder Xꢀray
diffraction (Fig. S2), UVꢀvis DRS (Fig. S3), time courses of phenol
4 | J. Name., 2012, 00, 1-3
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