Inorganic Chemistry
Article
compound 1, the reactions of methyl oleate (Ole) and DL-
limonene (Lim) give methyl 9,10-epoxystearate and 1,2-epoxy-
p-menth-8-ene as the main products in yields of up to 98% and
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8
9%, respectively (24 h, 75 °C). For Ole epoxidation, the
catalytic results for 1 are in the midrange of those reported for
other mono-/polynuclear molybdenum compounds possessing
2
(
9
3
2
(
bi)pyridine-type mono-/bidentate ligands, while, for Lim
epoxidation, 1 leads to comparable or even better results in
terms of epoxide yield. We have further shown that the catalyst
recycling issue can be successfully addressed by using an ionic
liquid as cosolvent with solvent extraction of the target epoxide
products between recycles.
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An attractive goal with molybdenum oxide/bipyridine hybrid
materials is heterogeneous catalysis, especially since the 1D
inorganic−organic chains present in the three materials
mentioned above can be considered as polymeric versions of
monomeric [MoO (OR) (bipy)] complexes, which are well-
3
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known as effective homogeneous olefin epoxidation catalysts.
As previously demonstrated for {[MoO (2,2′-bipy)]-
3
4a
[
MoO (H O)]} , the catalytic reaction may take place
3 2 n
heterogeneously by adjusting the reaction conditions (albeit
with relatively low activity, at least partly due to the low amount
of accessible active sites). There is a need to develop porous
molybdenum oxide/organic hybrid materials with improved
active site accessibility and that function as heterogeneous
catalysts. As supported by the present work, the introduction of
substituents on the organic ligands is one approach to expand
the structural complexity of these systems, and with further
work, this may lead to the preparation of supramolecular
frameworks with the desired properties.
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ASSOCIATED CONTENT
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Supporting Information
Detailed description of X-ray diffraction studies, Figures S1−S4,
Tables S1−S2, and crystallographic information file (CIF). This
(
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Gago, S.; Pillinger, M.; Goncalves, I. S.; Silva, C. M.; Valente, A. A.
Appl. Catal. A: Gen. 2011, 395, 71.
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AUTHOR INFORMATION
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Notes
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The authors declare no competing financial interest.
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ACKNOWLEDGMENTS
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(
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We are grateful to the Fundaca
FCT), QREN, Fundo Europeu de Desenvolvimento Regional
̧
o
̃
para a Cien
̂
cia e a Tecnologia
(
1
FEDER), COMPETE, and the European Union for funding
R&D Project No. PDTC/QUI-QUI/098098/2008, FCOMP-
1-0124-FEDER-010785). The Associate Laboratory CICECO
Pest-C/CTM/LA0011/2011) is acknowledged for continued
support and funding. We thank the FCT and the European
Union for a postdoctoral grant to P.N. (SFRH/BPD/73540/
Bordiga, S.; Bjørgen, M.; Tilset, M.; Lillerud, K. P. Chem. Mater. 2007,
19, 211. (c) Szeto, K. C.; Kongshaug, K. O.; Jakobsen, S.; Tilset, M.;
Lillerud, K. P. Dalton Trans. 2008, 2054. (d) Huh, S.; Jung, S.; Kim, Y.;
Kim, S.-J.; Park, S. Dalton Trans. 2010, 39, 1261. (e) Blake, A. J.;
Champness, N. R.; Easun, T. L.; Allan, D. R.; Nowell, H.; George, M.
W.; Jia, J.; Sun, X.-Z. Nat. Chem. 2010, 2, 688. (f) Bloch, E. D.; Britt,
D.; Lee, C.; Doonan, C. J.; Uribe-Romo, F. J.; Furukawa, H.; Long, J.
R.; Yaghi, O. M. J. Am. Chem. Soc. 2010, 132, 14382. (g) Long, J.;
Wang, L.; Gao, X.; Bai, C.; Jiang, H.; Li, Y. Chem. Commun. 2012, 48,
0
(
2
010), cofunded by MCTES and the European Social Fund
through the program POPH of QREN, and for a Ph.D. grant to
T.R.A. (SFRH/BD/64224/2009). We further wish to acknowl-
edge the European Synchrotron Radiation Facility (Grenoble,
France) for granting access time to the ID31 beamline under
the CH-3692 and CH-3702 research proposals.
1
2109. (h) Shen, L.; Gray, D.; Masel, R. I.; Girolami, G. S.
CrystEngComm 2012, 14, 5145. (i) Gustafsson, M.; Su, J.; Yue, H.;
Yao, Q.; Zou, X. Cryst. Growth Des. 2012, 12, 3243.
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dx.doi.org/10.1021/ic400248m | Inorg. Chem. 2013, 52, 4618−4628