Polyhedron Vol. 6, No. 2, pp. 213-218, 1987 0277-5387187 S3.00+.

00
Printed in Great Britain 0 1987 Pergamon Journals Ltd

ANDERSON-TYPE HETEROPOLYANIONS OF
MOLYBDENUM(W) AND TUNGSTEN(W)

KENJI NOMNA, TAKE0 TAKAHASHI, T AKAHIRO SHIRAI and

MAKOTO MIWA*
Department of Industrial Chemistry, Faculty of Engineering, Seikei University, Musashino,
Tokyo 180, Japan

(Received 7 April 1986 ; accepted 28 May 1986)

Abstract-The previously reported preparation of some Anderson-type molybdopoly-

anions containing divalent metal ions (Zn, Cu, Co or Mn) as a heteroatom has been
reinvestigated. The molybdopolyanions of Zn(I1) and Cu(I1) were contied, although
the Cu(I1) polyanion was not stable and could not be recrystallized. On the other
hand, the polyanions of Co(I1) and Mn(I1) could not be reproduced. Another type of
heteropoly compound, D((H,O),_.(MO,O~~)]~- [x = Cu(II), Co(II) or Mn(II)], was
isolated as solids, which are not stable thermally. The mixed-type Anderson polyanions,
~i(II)Mos_,WX024H,]4-, which have been questioned as mixtures of species with differ-
ent x values, were also reinvestigated using IR, UV absorption and MCD spectra. They
are single species, but not mixtures, although some positional isomers may be present for
the compounds where x = 2-4. The possibility of oxidation of the heteroatom with the
Anderson structure maintained was examined. The oxidation of [Ni(II)Mo602fis]4- by
the SzOi- ion in aqueous solution gave the Waugh-type ~i(Iv)Mo,032]6- polyanion,
whereas the oxidation of [Ni(II)W,024Hd4- gave no heteropoly compound.

Anderson-type heteropolyanions, represented by scopic (IR, UV absorption and MCD) methods of

the general formula ~M,O,,H,l-, possess a the mixed-type Ni(I1) molybdotungstopolyanions
heteroatom (X) in a central octahedral cavity previously reported by Matijevic et ~1. The last
of the crown by edge-sharing six octahedral MO6 concerns the possibility of the oxidation of Ni(I1)
(M = MO or W). These polyanions become a fam- molybdo- and tungstopolyanions leading to the cor-
ilyforanumberof2+,3+,4+,6+ and7+ metal responding Ni(IV) ones with the polyanion struc-
ions as the heteroatom. They have been classified ture maintained.
into A (x = 0) and B (X = 6) types by the number of
attached protons, although some polyanions with x
other than 0 or 6 have been recently reported.2*3 EXPERIMENTAL
Most of them have been tabulated in books..4 How-
Electronic absorption spectra were measured by
ever, some questionable compounds are also
a Hitachi 340 spectrophotometer with an attached
involved there. In this work, we have done three
computer-key board. MCD spectra were recorded
experimental studies. The first is related to members
by a JASCO J-40AS spectropolarimeter mounted
of the family of B-type molybdopolyanions,
with a lO.O-kG electromagnet. IR spectra were re-
especially the polyanions containing some divalent
corded with a JASCO IR-G spectrophotometer.
metal ions [Zn(II), Cu(II), Co(I1) or Mn(II)] other
Measurements were made at room temperature.
than Ni(II), which have been tist reported by
LaGinestra et al., and later questioned by Malik
et al6 The second is a reinvestigation by spectro- Preparations

WHWWW@d-bl~ 7W3 and W-bMX-

*Author to whom correspondence should be addressed. (II)Mo,O,,Hd - 5H,O. B-type molybdopolyanions
213
214 K. NOMIYA et al.
containing tervalent metal ions (Cr, Al or Fe) and water), filtering the yellow insoluble precipitate
Ni(I1) ion were obtained as crystals by the tra- produced, cooling the filtrate, and adding excess
ditional method :* adding an aqueous solution amounts of acetonitrile. The light blue solid
of metal sulphates or alums (3.1 x low3 mol) in obtained was insoluble in water and not stable
20 cm3 water into a boiling aqueous solution thermally. The Co(II) and Mn(I1) compounds were
of (NH.&Mo~O~~ - 4Hz0 (5 g, 4.2 x low3 mol) dis- not obtained from boiling solutions. Any changes
solved in 80 cm3 water, further evaporating on a in the pH of the initial heptamolybdate solution
steam-bath, filtering the hot solution and cooling. and in the reaction time gave mixtures of the initial
In the preparation of the Co(II1) polyanion, a materials and the bluish violet [for Co(H)] or yellow
mixed aqueous solution (30 cm3) of CoSO, - 7H,O [for Mn(II)] insoluble solids. On the other hand,
(4.2 g, 0.015 mol) and 30% aqueous HzOz (2 g) was from the experiments without boiling, the Cu(II),
added into the boiling solution of aqueous hepta- Co(I1) and Mn(II) compounds could be obtained,
molybdate (30.9 g, 2.5 x lo- mol in 260 cm3 which were insoluble in water and not stable ther-
water). These compounds were recrystallized twice mally. They were prepared by concentrating the
from water. The colour and analytical data are mixed aqueous solutions of the metal sulphates and
listed in Table 1. Visible absorption spectra of the heptamolybdate without heating and/or adding
Co(III), Cr(II1) and Ni(I1) compounds are in good excess amounts of acetonitrile. However, their
agreement with the previous data.g When the spectra were not identical with the characteristic
colourless Fe(II1) polyanion was dissolved in water, IR spectra of the Anderson molybdopolyanions.
the solution was a wine-red colour due to the dis- (NH&Ni(II)Mo,_,W,O,H,] * 5H20. B-type
sociation and/or the hydrolysis. Ni(II) molybdotungstopolyanions (x = 1,3,5 or 6)
The preparation of B-type Anderson molybdo- were prepared according to two methods of Mati-
polyanions containing divalent metal ions (Ni, jevic et al. Method 1 is based on the dropwise
Zn, Co or Mn) has been reported by LaGinestra et addition of an aqueous solution of Ni(II) sulphate
~1.~However, some questionable points were seen. into boiling solutions containing appropriate molar
They stated that such polyanions must be prepared ratios of MO and W, where the source of MO is
without boiling: however, the Ni(I1) and Zn(I1) (NH.&Mo70z4 * 4Hz0 for x = 0, Na,MoO, - 2H,O
compounds were actually obtained from boiling for x = 1, and Moo3 for x = 2-5 ; and the source
solutions. The Zn(I1) compound was obtained as of W is Na*WO., - 2Hz0 for all x. Method 2 is
colourless crystals by adding an aqueous solution based on heating above 80C aqueous solutions
of ZnS04 * 7Hz0 (1 g, 3 x 1OT3mol in 20 cm3 water) containing appropriate molar mixtures of already
into a boiled solution of heptamolybdate (5 g, isolated x = 0 or 6 compounds, and cooling spon-
4.2 x 10e3 mol in 80 cm3 water). It was recrystallized taneously to room temperature. All compounds,
twice from water. Analytical data are listed in Table recrystallized twice. from water, were obtained as
1. This compound was very soluble in water. sky-blue crystals. Analytical results for all the
Further, the Cu(I1) compound was obtained by compounds were in good agreement within the
adding Cu(I1) sulphate solution (0.75 g, 3 x 10e3 experimental error. However, they do not lead
mol in 20 cm3 water) into the boiled solution of to direct evidence for these mixed species, because
heptamolybdate (5 g, 4.2 x 10e3 mol in 80 cm3 they cannot be discriminated from those of
mixtures of species with different compositions.
(Na, K),[Ni(IV)W,O$ * nHzO. An A-type
Ni(IV) tungstopolyanion was obtained by the
Table 1. Colour and analytical data for (NH&X(III) modification of the preparation of the isostruc-
Mo60xH6] - 7H,O and (NH&X(II)Mo,O,H,] * 5Hz0 tural Mn(IV) tungstopolyanion. A solution of
Na2W04 * 2H,O (20 g, 0.06 mol) in 100 cm3 water
Found Calculated was boiled, into which NiSO,* 6Hz0 (2.6 g, 0.01
(%) (%) mol) in 10 cm3 water was slowly added. Further, a
fine powder of K&O,, (5.4 g, 0.02 mol) was added.
X Colour NH NH The boiling was continued for about 15 min, with
occasional additions of water. The reaction mixture
Co(II1) Blue-green 2.4 3.6 2.7 3.5
was poured into an equal amount of hot water and
Cr(II1) Reddish-violet 2.4 3.6 2.7 3.5
the solution kept at 80C for about 30 min on the
Fe(II1) Colourless 2.4 3.6 2.7 3.5
Al(II1) Colourless 2.4 3.7 2.7 3.6
steam-bath. The black crystals formed were filtered,
Ni(I1) Sky-blue 2.7 4.6 2.7 4.7 washed with water, and dried (yield 2.5 g). This
Zn(I1) Colourless 2.3 4.5 2.7 4.7 compound was slightly soluble in water and insol-
uble in most other solvents.
 Anderson-type heteropolyanions of molybdenum(V1) and tungsten(W) 215

Oxidation of Ni(II) molybdo- and tungstopolyanions

When an aqueous solution of (NH,),[Ni(II)

Mo60z4H6] - 5Hz0 containing (NH&SzOs was
heated, a colour change was seen ; from sky-blue it
turned gradually to black. After the homogeneous
black solution was left standing at room tempera-
ture, the colourless precipitates produced were
filtered off. The black crystals obtained from
the filtrate showed IR spectra identical with
that of the Waugh-type heteropoly compound
(NH&Ni(IV)Mo,O,,], which was prepared sep-
arately.13 On the other hand, in the analogous
experiments using (NH,)JNi(II)W,O,H,] * 5Hz0,
no heteropoly compound could be obtained. In
this reaction, the solution became blackish via
yellowish-brown, but then it turned to green.
Further addition of (NH&S208 showed no more
colour change. Only the mixture of decomposed
materials was given.

RESULTS AND DISCUSSION

B-type molybdopolyanions with divalent metal ions 1000 600 600 4 0

as a heteroatom (cm-)

In the Anderson heteropolyanion, each hetero- Fig. 1. Solid IR spectra of Anderson-type

atom forms an octahedral complex of six oxy-
gens for A-type and of six OH groups for B-type.
Thus, the visible absorption spectra of B-type poly-
anions of Co(III), Cr(II1) and Ni(II) are com-
parable with that of the corresponding hexaaqua
complexes,g although the peak intensities of the
polyanions are smaller as shown in Table 2. IR
spectra of Anderson-type ~(III)Mo,O,,H,]~-
[x(111) = Co(III), Cr(III), Fe(II1) or AI(III)] are
presented in Fig. 1. The bands due to the hetero-
atom are seen only in the region less than 450
cm-. Since the IR spectra in the 950-900- and 65&
P(III)Mo~O~~HJ~- polyanions.
550-m- regions become independent of the sort
of heteroatom, they can be said to be in the
pattern common to the B-type Anderson mol-
ybdopolyanions. In fact, the Ni(II), Zn(I1) and
Cu(I1) molybdopolyanions show the characteristic
IR spectra (Fig. 2). The IR spectrum previously
shown for the Mn(I1) compound by LaGinestra
et al. is evidently different from these patterns.

Table 2. Spectral data of visible and near-IR absorption of Anderson-type

molybdopolyanions of Co(III), Cr(II1) and Ni(I1)

I. (x lo- cm-) (&)

[Co(III)Mo,0,H,13- 16.5 (18.6) 24.2 (18.4)

[CO(H~O)J~+~ 16.5 (40) 25.0 (50)
[Cr(III)Mo,O%H J3- 18.5 (7.8) 25.3 (9.5)
[Cr(HA%13+ LI 17.4 (13.3) 24.6 (15.3)
[Ni(II)Mo,OxH$- 9.3 (1.6) 13.7 (1.2) 15.6 (1.8)
lWH@M* a 8.5 (2.0) 13.8 (2.1) 15.2 (1.9)
[SiNiMo, ,0,H,]6-b 8.6 (5.3) 14.5 (6)

Ref. 10.
Ref. 11.
216 K. NOMIYA et al.
1000 800 600 8 600
km-
Fig. 2. Solid IR spectra of Anderson-type
[x(II)Mo,0,H,J4- polyanions.
Although they have attributed the disagreement to
the different formulae due to the number of
hydrates, it presumably accounted for the com-
pound itself. On the other hand, the IR spectrum
presented by them as that of the Co(I1) compound
is apparently similar to the characteristic patterns.
We have occasionally obtained the compound
showing such an IR spectrum from the reaction
involving boiling with a Co(II) sulphate solution
and an aqueous heptamolybdate solution adjusted
to pH 4.46. However, such a compound was a
minor product.
The Cu(II), Co(I1) and Mn(I1) compounds
obtained from the experiments without boiling were
not of the Anderson type, but like the Mo70z4 poly-
anion. These compounds showed IR spectra very
similar to that of the [Mo~O~~]~-polyanion, except
for the slightly broad bands in the 650-550~cn-
region and the ca 10 cm- shift to the high-fre-
quency region of the bands at cu 900 cm- (Fig.
3). They were insoluble in water and could not be
recrystallized. Heating the aqueous suspension led
to decomposition. These compounds are probably
the D((Hz0)6_,(M07024)]4--type 1 : 1 complex,
which was first proposed by Malik et a1.,6
600 400
(cm?
Fig. 3. Solid IR spectra of the 1: 1 metal ion
(X): Mo,O;; complexes and Mo,O& alone (on the
bottom).
from the Job method of continuous variation
in an aqueous solution of metal sulphate and
heptamolybdate. As a related complex, we have
previously isolated the 1 : 2 Ce(II1) : Mo70z4 com-
plex as orange-red crystals from an aqueous
solution containing ammonium Ce(II1) nitrate and
ammonium heptamolybdate.14,5 The preparation
was done only at room temperature, and the Ce(II1)
complex obtained was also insoluble in water, and
not stable thermally.
The Anderson heteropolyanion is one of the most
well-known polyanions and it constitutes a family
with a number of heteroatoms.*4 We propose that
the Co(I1) and Mn(I1) ions should be excluded from
the Anderson family and entered into another
category of polyanion.
Mixed-type [Ni(II)M06_,W,o,H6]- polyanions
For these mixed polyanions, the possibility has
been pointed that they are mixtures of polyanions
with different x values. However, it was easily
confirmed from the IR spectra that the x = 3 com-
pound obtained by method 1 differed from an equi-
molar mixture of the x = 0 and x = 6 compounds.
 Anderson-type heteropolyanions of molybdenum(V1) and tungsten(V1) 217

Further, the IR spectra of the x = 3 compounds
obtained by methods 1 and 2 were identical, as
shown in Fig. 4. The IR spectra of each mixed
polyanion were subtly different, and all of them
resembled that of the x = 6 rather than the x = 0
compound as a whole.
In aqueous solution, these mixed polyanions
showed the behaviour of a single species. Figure 5
shows the W and MCD spectra of the x = 0, 1,3,
5 and 6 compounds obtained by method 1. MCD
spectra evidently indicate that they are single
species, but not a mixture of species with different
compositions, because the peak positions are quite
different.
We can see some implications for the formation
of the mixed Anderson cage in the experiments by
method 2, and also in the recrystallization process
for the x = 0 and x = 6 compounds. When an aque-
ous solution containing the Ni(I1) Anderson poly-
anion is heated above 8OC, a colour change of the
solution is observed from sky-blue to green. During
the cooling process to room temperature, it returns
to the original sky-blue. The green solution will be
due to the Ni(I1) aqua ion produced by dissociation
of the polyanion. Therefore, it seems that, during
the cooling process, the Anderson cage is formed
around the Ni(II) ion as a core. The mixed
Anderson cage will be formed on the basis of the
reorientation of randomly distributed MO and
W 0x0 ions at the high temperature. Thus, the
experiments by two methods do not exclude the
possibility that the x = 3 compound, and also the
x = 2 and x = 4 compounds, contain some posi-
tional isomers.
Oxidation of Ni(II) molybdo- and tungstopolyanions
The oxidation of the [Ni(II)Mo60z4HJ4- poly-
anion by the SzOi- ion in aqueous solution led to
the formation of a Waugh-type [Ni(IV)Mo,0,,16-
polyanion, which was isolated separately.13 The val-
ency of the heteroatom can be changed and the
polyanion cage is simultaneously transformed. On
the other hand, the oxidation of [Ni(II)W&H6]4-
gave the decomposition mixture, but no heteropoly
compound. The same initial materials have been
used in the preparations of [Ni(rv)W@z4]8- and
[Ni(II)w6024H6]4- pdyauhs, except for the

1200 1000 800 600 400 600 400

(cmd) (cm)
Fig. 4. Solid IR spectra of [Ni(II)Mo,_,W,O,J5$ polyanions; x = 6 (A) and 0 (B) compounds,
equimolar mixture (A + B) of them, and x = 3 compounds obtained by methods 1 (C) and 2 (D).
218 K. NOMIYA et al.

which proceed by the outer-sphere mechanism of

an electron transfer. 18*ig
In this case, the Anderson
structure may be thermally less stable than the
Keggin structure.

REFERENCES
M. T. Pope, Heteropoly and Zsopoly Oxometalates.
p. 21. Springer, New York (1983).
U. Lee, A. Kobayashi and Y. Sasaki, Acta Cryst.
1983, C39,817.
U. Lee and Y. Sasaki, Chem. Lett. 1984,1297.
.Y F. A. Cotton and G. Wilkinson, Advanced Inorganic
0 Chemistry, 4th Edn, p. 852. John Wiley, New York
;i
W (1980).
2 5. A. LaGinestra, F. Giannetta and P. Fiorucci, Gazz.
Chim. Ital. 1968,98, 1197.
6. A. Malik, S. A. Zubaili and S. Khan, J. Chem. SOL,
Dalton Trans. 1977, 1049.
t- 7. E. Matijevic, M. Kerker, H. Bayer and F. Theubert,
Znorg. Chem. 1963,2, 581.
8. R. D. Hall, J. Am. Chem. Sot. 1907,29,692.
9. Y. Shimura, H. Ito and R. Tsuchida, Nippon Kagaku
I I
o- Zasshi 1954,75,560.
25 30 35 40 45 . 50 10. D. Sutton, Electronic Spectra of Transition Metal
10Jcm-l Complexes. McGraw-Hill, New York (1968).
11. S. A. Malik, J. Znorg. Nucl. Chem. 1970,32,2425.
Fig. 5. UV absorption and MCD spectra of
12. V. S. Sergienko, V. N. Molchanov, M. A. Porai-
[Ni(II)Mo~_xWxOxH,]4- polyanions : x = 0 (----),
Koshits and E. A. Torchenkova, Koord. Khim. 1979,
x=1 (-----), x=3 (-), x = 5 ( .e..), and
5,936; Sov. J. Coord. Chem. (Engl. Trans.) 1979,5,
x = 6 (----).
740.
13. K. Nomiya, R. Kobayashi and M. Miwa, Polyhedron
1985,4, 149.
addition of the SzOg- ion in the former. Thus, this 14. M.-J. Schwing-Weill, Bull. Sot. Chim. Fr. 1972,1754.
oxidation experiment suggests that the formation 15. K. Nomiya, H. Murasaki and M. Miwa, unpublished
results.
of the [Ni(IV)W,O,,]- polyanion does not pro-
16. L. C. W. Baker and T. P. McCutcheon, J. Am. Chem.
ceed through the oxidation of the already formed
Sot. 1956,78,4503.
[Ni(II)W6024H6]4- polyanion. In a Keggin-type 17. K. Nomiya, R. Kobayashi and M. Miwa, Bull. Chem.
polyanion, the valency of the central heteroatom Sot. Jpn 1983,56,2272.
can be changed sometimes by chemical oxidation, 18. A. G. Lappin and R. D. Peacock, Znorg. Chim. Acta
with the polyanion structure maintained, such 1980,46, L71.
as [CO(II)W,,O,]~- + [CO(III)W,~O~]~- 16*17and 19. P. G. Rasmussen and C. H. Brubaker, Znorg. Chem.
[CU(I)W~~O~]- + [CU(II)W,~O~~]~-,~~ reactions 1964,3,977.