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Fig. 2 Positive ion CSI MS study of the reaction of 2-Fe and H
2
O
2
at À40 1C. Experimental (black) and simulated (red) isotopic distribution patterns of molecular peaks
+
+
+
of (a) [2-Fe + H] , (b) [2-FeQO + H] and (c) [2-FeÀOOH] .
2
3
(a) A. B. Sorokin and E. V. Kudrik, Catal. Today, 2011, 159, 37–46;
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(
2
2
005, 29, 1400–1403; (c) N. Sehlothi and T. Nyokong, J. Mol. Catal. A,
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(
Scheme 1 Proposed mechanism for the formation of high-valent iron oxo
helmet phthalocyanine species.
8
5
2
rapidly performed at À40 1C in the positive detection mode.
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Along with the signal of the starting complex at m/z = 711 (for
+
[
[
(
2-Fe + H] ) signals at m/z = 727 and m/z = 743 corresponding to
+
+
2-FeQO + H] and [2-FeÀOOH] , respectively, were observed
Fig. 2). While experimental isotopic distribution patterns of
+
+
molecular peaks of [2-Fe + H] and [2-FeÀOOH] species are
identical to theoretical ones, the comparison of experimental
and simulated molecular peak clusters of oxo species suggests a
contribution of several protonated forms. The experimental
isotopic distribution pattern of the molecular peak of the oxo
complex can be simulated suggesting the presence of B55%
of monoprotonated and B45% of diprotonated species. The
transient nature of this signal is compatible with the proposed
structure of high-valent iron oxo species capable of performing
the selective epoxidation of olefins. A possible mechanism of
formation of this species is proposed in Scheme 1.
8
3
326–3328; (c) E. S. Brown, J. R. Robinson, A. M. McCoy and
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1
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In conclusion, we have shown highly efficient mild epoxida-
tion of a range of olefins by H O mediated by iron helmet
2
2
phthalocyanines for the first time. The hydroperoxo and high-
valent iron oxo species based on the modified phthalocyanine
core were detected for the first time. The latter was proposed to
be involved in the selective epoxidation of olefins.
This work was supported by grant ANR-08-BLAN-0183-01
from Agence Nationale de la Recherche (ANR, France). I.Y.S.
thanks the French Embassy in Moscow for the doctoral fellow-
ship. O.V.Z. is grateful to Region Rh oˆ ne-Alpes for the post-
doctoral fellowship.
1
(
c) E. V. Kudrik and A. B. Sorokin, Chem.–Eur. J., 2008, 14, 7123–7126;
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2 P. Afanasiev, D. Bouchu, E. V. Kudrik, J.-M. M. Millet and
A. B. Sorokin, Dalton Trans., 2009, 9828–9836.
1
1
1
3 L. X. Alvarez, E. V. Kudrik and A. B. Sorokin, Chem.–Eur. J., 2011, 17,
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4 E. V. Kudrik, P. Afanasiev, L. X. Alvarez, P. Dubourdeaux,
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Notes and references
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Chem. Commun.