ChemComm
Communication
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An experiment using the non-acidic ((C4H9)4N)5PV2Mo10O40,
yielded little product presumably due to its lower oxidation
18
potential versus H5PV2Mo10O40
.
The effect of the presence of
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vanadium in the polyoxometalate was evaluated by comparing
reactivity of H3+xPVxMo12ÀxO40 for x = 0, 1, and 2 in the catalytic
epoxidation of cyclododecene. The reaction conditions were
0.43 mmol cyclododecene, 0.0043 mmol polyoxometalate (1 mol%),
0.43 mmol Na2SO3 at 65 1C in 1 mL AcOH under 2 bar O2, 1 h.
The relative efficiency as measured by the turnover number was
H5PV2Mo10O40 (58) 4 H4PVMo11O40 (19) 4 H3PMo12O40 (3), resem-
bling the order found for other reactions catalysed by phosphova-
nadomolybdates and is explained by the activity for electron transfer
oxidation: H5PV2Mo10O40 4 H4PVMo11O40 4 H3PMo12O40.14 Above
it was shown by Raman spectroscopy that peroxosulphate
species were formed. A reaction carried out with 18O2 (4.3 mmol
H5PV2Mo10O40, 0.43 mmol Na2SO3, 0.43 mmol cis-cyclooctene, 65 1C
in 1 mL AcOH, 1.5 bar 97% 18O2) yielded 495% 18-O labelled
cis-cyclooctene oxide, indicating that the persulphate intermediate
formed is also the oxygen donor.
In summary, a protocol has been developed for the in situ
formation of monooxygen persulphate from inexpensive Na2SO3/O2
using an inorganic polyoxometalate H5PV2Mo10O40 catalyst. The
reaction sequence, Scheme 1, has been delineated and oxygen
transfer to some representative alkenes has been quantified. The
insolubility of the by-product, Na2SO4, makes this protocol a
good alternative to the aldehyde/O2 method often used for in situ
peracid formation.‡ Future research will expand the reaction
scope to additional substrate types.
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Notes and references
‡ Specifically H5PV2Mo10O40 did not catalyse the epoxidation of cyclo-
dodecene with isobutyraldehyde/O2, that is 0.43 mmol cyclododecene, 18 P. Carloni and L. Eberson, Acta Chem. Scand., 1991, 45, 373–376;
0.0043 mmol H5PV2Mo10O40 and 0.43 mmol (CH3)2CHCHO at 65 1C in
1 mL AcOH or CH3CN under 2 bar O2 for 1 h yielded no product.
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87–91.
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