TY - JOUR
T1 - Distinctly different reactivities of two similar polyoxoniobates with hydrogen peroxide
AU - Ohlin, Christian Andre
AU - Villa, Eric
AU - Fettinger, James
AU - Casey, William
PY - 2008
Y1 - 2008
N2 - Niobium oxides are used as photocatalysts[1] and also used to
sequester radionuclides from waste.[2] Hydrogen peroxide is a
common byproduct from these applications, and herein we
examine how isopolyoxoniobates, the hexaniobate
[HxNb6O19](8 x) and the decaniobate [HxNb10O28](6 x) ions,
react with hxdrogen peroxide. Both the isopolyoxoniobate
and the peroxopolyoxoniobate species can be detected by
using electrospray-ionization mass spectrometry (ESI-MS)
and 17O NMR spectroscopy. Interestingly, we observed that
although the decaniobate anion rapidly picks up peroxide, the
peroxodecaniobate clusters can dissociate over time and yield
the peroxohexaniobate species, and sometimes in the presence
of reformed and peroxy-free decaniobate ion. In both
isopolyoxoniobate structures, the reaction proceeds by the
replacement of niobium terminal oxygen atoms with h2-
O(I)22 . The peroxohexaniobate species are extraordinarily
stable and we have determined the crystal structure of
[N(CH3)4]5[H3Nb6O13(O(I)2)6]A?9.5H2O, in which all six terminal
oxygen atoms are replaced by h2-O(I)22 . This crystal
structure us the first example of an isolated peroxoisopolyoxoniobate
cluster.
AB - Niobium oxides are used as photocatalysts[1] and also used to
sequester radionuclides from waste.[2] Hydrogen peroxide is a
common byproduct from these applications, and herein we
examine how isopolyoxoniobates, the hexaniobate
[HxNb6O19](8 x) and the decaniobate [HxNb10O28](6 x) ions,
react with hxdrogen peroxide. Both the isopolyoxoniobate
and the peroxopolyoxoniobate species can be detected by
using electrospray-ionization mass spectrometry (ESI-MS)
and 17O NMR spectroscopy. Interestingly, we observed that
although the decaniobate anion rapidly picks up peroxide, the
peroxodecaniobate clusters can dissociate over time and yield
the peroxohexaniobate species, and sometimes in the presence
of reformed and peroxy-free decaniobate ion. In both
isopolyoxoniobate structures, the reaction proceeds by the
replacement of niobium terminal oxygen atoms with h2-
O(I)22 . The peroxohexaniobate species are extraordinarily
stable and we have determined the crystal structure of
[N(CH3)4]5[H3Nb6O13(O(I)2)6]A?9.5H2O, in which all six terminal
oxygen atoms are replaced by h2-O(I)22 . This crystal
structure us the first example of an isolated peroxoisopolyoxoniobate
cluster.
UR - http://onlinelibrary.wiley.com/doi/10.1002/anie.200803688/pdf
U2 - 10.1002/anie.200803688
DO - 10.1002/anie.200803688
M3 - Article
VL - 47
SP - 8251
EP - 8254
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
SN - 1433-7851
IS - 43
ER -