J. lnorg. Nucl. Chem., 1966, Vol. 28, pp. 447 to 454. Pergamon Press Ltd.

Printed in Northern Ireland

THE STABILITIES OF THE 9-MOLYBDOMANGANATE (IV)

AND 9-MOLYBDONICKELATE (IV) IONS
L. C. W. BAKER
Georgetown University, Washington 7, D.C.
and
T. J. R. WEAKLEY
Queen's College, Dundee, Scotland
(Received 15 June 1965)

Abstract--The isostructural hetero-9-molybdat ions are stable monomers at high concentrations in

saturated aqueous Na~SO~. They are only slightly solvated. Some decomposition occurs in more
dilute solutions. (MnMogOsIP- is decomposed above pH 5; (NiMosOsiP-, above pH 5.5. Unstable
H6(MnMo0Oa2)hasbeenpreparedinaqucoussolution. Successivc pK's are close together. Comments
are made on the spectra of the two complexes.
THE hetero-9-molybdate anions have the general formula [MMogOa2] e-. The Ni (IV)
and M n (IV) complexes were first reported by HALL, (1) together with a Co (IV)
complex whose existence has since been disproved. (2) The [MnM09032] 6- ion is
always f o r m e d in any attempt to prepare m o l y b d o m a n g a n a t e s (III) or (IV). (2'3'4)
The a m m o n i u m salts are i s o m o r p h o u s ; they crystallize as plain r h o m b o h e d r a and
also as r h o m b o h e d r a with additional faces conferring left- and right-handedness.
A n X - r a y structure determination (5) has shown that the [MnMogO32P- ion has D3
symmetry and is based on a M n O e octahedron. The nickel complex is diamagnetic, (e)
as should be the case for a d 6 ion in a strong-field octahedral environment. The
spectra o f b o t h complexes have been reported. (4'7"s) The present work was undertaken
to investigate the stabilities o f these complex ions towards dissociation, hydrolysis
and racemization.
EXPERIMENTAL
The ammonium salts were prepared by a modification of Hall's method, (1) using ammonium
peroxydisulphate or (for the manganese complex only) hydrogen peroxide as oxidant. A large excess
of oxidant was undesirable in the preparation of the nickel complex, which is attacked by the decomposition products of S2Od- ion. The best yields were obtained by adding a solution of MnSO4 or
NiSO4, containing the oxidant, to a slight excess of 10 ~ (NH4),MoTO,4 solution at 95; the mixture
was boiled and stirred for five minutes, and quickly filtered and cooled. The orange-red (Mn) or
red-black (Ni) crystals were recrystallized three times from hot water (70); [NiMogOsde- ion could,
however, only be freed from small amounts of cationic nickel by passing a solution through a cationexchange column in the sodium form. The oxidation states of the betero-atoms were confirmed by
(t) R. D. HALL,J. Amer. Chem. Soc. 29, 692 (1907).
(2) G. A. TSlGDINOS,Ph.D. thesis, Boston University (1961).
(s) p. Soucvo, Y and A. TCI~aC~AN, Ann. Chem. 1, 249 (1946).
(4) p. SoucrLcv and R. SCH.~,L, Analyt. Chim. Acta 3, 1 (1949).
(5) D . P . SHOEMAKER, J. L . T. WAUGFI and L. PAULr~G,Acta Cryst. 7, 438 (1954).
(s) p. RAY, A. Bm~DtrPaand B. SARMA,J. Indian Chem. Soc. 25, 51 (1948).
(7) y. SmMugA, H. ITO and R. TSUCHmA,J. Chem. Soc. Japan 75, 560 (1954).
(s) C. K. JOROENSEN,Acta Chem. Scand. 12, 1539 (1958).
447

448

L . C . W . BAKER and T. J. R. WEAKLEY

reducing the complex with an excess of oxalic acid or of acidic As (III) solution and back-titrating.
Solutions of the sodium salts, and of 9-molybdomanganic acid, were prepared by ion exchange, ~D~
The ammonium salt was recovered from the acid in low yield by adding dilute ammonia to pH 4.5,
and saturating with ammonium nitrate. Its X-ray powder pattern was identical with that of a sample
prepared as described above.
Solutions for viscosity measurements were concentrated in cellophane bags in an air current at
room temperature. Viscosities were measured with an Ostwald viscometer at 25 -4- 0.1; kinetic
energy and density corrections were applied.
Transition-point temperatures in fused NasSO~.10H~O were measured to +0.001 with a Beckmann thermometer in a vacuum-jacketed 20 3 cm tube. ~'x~ Mixtures were prepared by adding
15.0 g anhydrous Na~SO~ to 20 ml portions of solutions of the sodium salts, analysed for molybdenum and the hetero-element.
Instruments employed included a North American Philips recording X-ray powder diffractometer;
Beckmann DU and Unicam SP.700 spectrophotometers for solution work; a Hilger and Watts H.700
spectrophotometer with powder reflectance attachment; and a Leeds and Northrop 7662 pH meter.
Potentiometric titrations were performed as described elsewhere. ~m
Attempts were made to resolve both the complex anions. The methods tried were:
(1) Selective absorption on optically-active quartz. ~m
(2) Selectively reducing one enantiomorph by D-tartrate and D-antimonyl tartrate.
(3) Inducing a first order asymmetric transformation cxs~in the presence of D-camphorsulphonate
ion.
(4) Growing large single asymmetric crystals of the ammonium salts.
(5) Forming diastereoisomers with optically active cations (o- and L-1:2-diammonium propane,
D- and L-~-phenylethylammonium, D-Coena 8+, cinchoninium). These ions, however, form
very insoluble salts with heteropolyanions, from which it is difficult to displace the active
cation.
The optical rotation of each test solution (about 10-8 M) was examined at several wavelengths
between 400 m/~ and 650 in#, using a modified Beckmann DU spectrophotometer similar to that
described by KmSCHNER.tt4~ Rotations of 0"004 could be detected.
RESULTS
C r y s t a l i s o m o r p h i s m a n d chemical analysis suggests t h a t the h e t e r o - 9 - m o l y b d a t e
ions are isostructural. This is c o n f i r m e d b y the identical line p o s i t i o n s a n d very
similar intensities in the X - r a y p o w d e r d i a g r a m s o f the a m m o n i u m salts.
B o t h complexes are r e d u c e d b y iodide, arsenite, o x a l a t e o r sulphite in n e u t r a l o r
slightly acidic solution. M n ~+ a n d [NiMo6024H6] 4- ions are formed. T h e latter was
p r e c i p i t a t e d as the a m m o n i u m salt, t2~ which was identified b y its X - r a y p o w d e r
p a t t e r n . T h e N i (IV) c o m p l e x also oxidizes h y d r o g e n p e r o x i d e a n d (in acid m e d i u m )
water. T h e kinetics o f the latter process are being studied. Consequently, 9 - m o l y b donickelic acid c a n n o t be p r e p a r e d ; b u t the very soluble 9 - m o l y b d o m a n g a n i c acid
is sufficiently Stable for a n a q u e o u s s o l u t i o n to be p r e p a r e d b y ion-exchange.
~g~L. C. W. BAKER,B. LOEVand T. P. McCUTCHEON, J. Amer. Chem. Soc. 72, 2374 (1950).
tl0~ L. C. W. BAKER,M. T. POPEand G. A. TSmDrNOS,Abstracts, Div. of Inorg. Chem., Amer. Chem.
Soc. meeting, Boston, April 1959.
cxt~L. C W. BAKER,G. A. GALLAGrmRand P. T. McCuTcrmora, J. Amer. Chem. Soc. 75, 2493 (1953);
L. C. W. BA~:ER, G. FOSaZR, W. TAN, F. SCHNOLNICKand T. P. McCtrrcHEON, Ibid. 77, 2136
(1955).
c~2~See references given by WmKms and WmLt~MS in LEWIS and WmKrNs' Modern Coordination
Chemistry, p. 205, Interscience, New York (1960).
ltnl F. BASOLOand R. B. PEARSON,Mechanisms of Inorganic Reactions, p. 285, J. Wiley, New York
(1958).
~x4~S. Kmscm~R, A. J. SONr,mSSA,D. C. BrIATNAOARand D. MoYu, Abstracts, Div. of Inorg. Chem.,
Amer. Chem. Soc. meeting, New York, Sept. 1960.

The stabilities of the 9-molybdomanganate(IV) and 9-molybdonickelate(IV) ions

449

The use of fused-hydrate cryoscopy to ascertain the formula weights of heteropolymolybdates has been described previously, tx~ Figure 1 summarizes the results
obtained in this work. The molarities are those of the aqueous solutions to which
anhydrous Na2SO4 was added (previous section). The limiting value of AT/c (1.93
degree-litre-mole -x) obtained by extrapolation from the higher concentrations is that
found for sodium salts of known formula weight. The increase in AT/c at low
concentrations is comparable with the experimental error and probably exaggerates
the degree of dissociation of the complex anions.

2.2
o

________.<r-~ o -

--q-~--~--~~.

2.0

1.8

o h4n

eNi

1'6

0'02

'

0"()4

0'06

0"08

0"10

c (molar)
FIG, 1 . - - F u s e d N a ~ S O 4 - 1 0 H 2 0 c r y o s c o p y ;

sodium hetero-9-molybdates.

The pH titration curves for the Mn complex are shown in Fig. 2. The initial pH
for the ammonium salt cannot be ascribed entirely to hydrolysis of the cation, but
must imply that some attack on the anion by solvent has occurred. The species first
formed cannot be identified, but the overall equation for hydrolysis would be:
7MnMogOa2 ~ + 6H20 -+ 7MnO2 + 9Mo70~46- + 12H+
(this reaction is reversible; if freshly-precipitated MnO2 is digested with hot paramolybdate, the [MnMogOz2] 6- ion is formed). The plateau in each titration curve
shows that the anion is largely decomposed above pH 5. The end point at 12 O H per anion is that expected for complete degradation to MnOz and MoO4~-.
The neutralization curve for the acid varies slightly from one preparation to
another. Evidently some decomposition takes place. Two typical curves are shown;
these indicate that successive dissociation constants are all in the range 10-2-10 -z M.
The first end point is observed after the addition of 5-5.5 (not 6) equivalents of base,
possibly because degradation of the anion sets in before neutralization is complete.
The titration curve for (NH~)rNiMogO32 (not shown) is similar to that for the
manganese compound, except that base attack occurs around pH 5.2-5.5.
Viscosity data are shown in Fig. 3. ~Tspis the fractional increase in viscosity caused
by the solute. For 6-molybdocobaltic acid ~1~)the equation ~16~
~Tsp = Ac 1/~ + Bc
t15~ L. C . W . BAKER a n d M . T. POPE, d. Phys. Chem. 63, 2083 (1959).
~16~ G . JONES a n d M . DOLE, d. Amer. Chem. Soc. 51, 2950 (1924).
12

450

L . C . W . BAKES and T. J. R. WV,AKLeY

lo

pH
6

~'~

~6

20

0 H-~Mn
Fxo. 2.--pH titrations. (1) (NH4)s[MnMosOn], 1"10 x 10-s M. (2) free acid, 3.73 X
10 -s M; (3) free acid, 2.91 10-s M.

1.o

0.8

0-6

~sp
0.4
"

0.2

0.1

0.2

0.3

Molarity

FIG. 3.--Viscosity measurements. Ordinate: specific viscosity. (1) He[IVlnMo.Oss];

(2) sodium salts; (3) limiting slope, curve 2.

The stabilities of the 9-molybdomanganate(IV) and 9-molybdonickelate(IV) ions

451

holds good, with A equal to zero; but the data for sodium 9-molybdomanganate
and 9-molybdonickelate, and for 9-molybdomanganic acid, cannot be fitted to this
equation. The acid is somewhat decomposed; but the limiting slope of the plot of
~?sp against c for the sodium salts can be used to estimate the hydrodynamic volume
of the anions. We assume that at low concentrations
~Tsp = B c

where B, according to GURNEY,t17) is the sum of contributions from individual ions.

C) ~

50

40

30

20

Fro. 4.--Spectrum of(NH4)dMnMogOss]. Abscissa,frequency(103cm-1). (1) powder

reflectance; ordinate,absorbance (arbitrary units). (2) solution; ordinate, log e.
In this instance, B = 2.0 litre-mole-I. For Na +, B = 0.086 litre-mole-1; whence for
the heteropolyanions B = 1.5 litre-mole-1. It has been shown cxS,~s~that for ions of
this type the Einstein viscosity equation may then be applied to obtain the hydrodynamic volume. For the hetero-9-molybdate ions this volume is approximately
100 A a, corresponding to a diameter of 12-12.5/~.
The solution and diffuse reflectance spectra (Figs. 4 and 5) indicate that the species
present in the crystals largely persist in aqueous solution. The complete spectrum of
the manganese complex, showing the "ruby" band at 14,300 em-1 (700 nap) has not
,1" R. W. GURm~Y,Ionic Processes in Solution, McGraw-Hill,New York (1953).
~ts~T. Ktmucs~v,A. M. SAROV.SONand B. D. W~'T,d. Phys. Chem. 61, 1567 (1957).

452

L.C.W. BAKERand T. J. R. WrAKLEY

been published before. The log ~ values in the ultra-violet are only approximate, as
both complex anions show slight deviations from Beer's law (both in pure water and
in buffered solution), the sign of the deviation depending on the wavelength. The
maximum near 25,500 cm -x is seen when concentrated solutions are examined in
0-1 cm ceils, but is masked in dilute solutions by the steeply-increasing absorbance in
the ultra-violet.

5 0L

4 ~0

'

3'0

'
20

FIG. 5.--Spectrum of (NH4)s[NiMogOs2]. Abscissa,frequency (10s cm-1). (1) powder

reflectance; ordinate, absorbance (arbitrary units). (2) solution; ordinate, log ~.
The form of the spectrum of the Ni complex in the visible region is little affected
by the pH in sodium acetate-acetic acid buffers, but the intensity falls off with time
as water is oxidized by the Ni (IV). In contrast, the form of the spectrum of the Mn
complex depends markedly on the pH (Fig. 6) but shows little change with time. At
higher pH's only a shoulder is seen, and hydrous MnOz is slowly deposited.
The spectrum of H6[MnMogO32] is similar to that of the ammonium salt at pH
2.9. As the pH is raised, by the cautious addition of sodium acetate solution, the
absorbance increases until MnO~ appears, but the characteristic double peak is not
seen.
Attempts to resolve the complexes were all unsuccessful. In experiments where
the test solution contained an optically-active species with a normal dispersion curve
there was no sign of a superimposed Cotton effect that could be associated with the

The stabilites of the 9-molybdomanganate (IV) and 9-molybdonickelate (IV) ions

453

absorption bands of the complexes in the visible region. The low concentrations-about 10-8 M - - o f the strongly-absorbing complexes must be remembered.

0.5

0-4

0.3

0.2

0.1

O ~

400

500

600 rn/~

FIG. 6.--Spectrum, (NH4)8[MnMogOs2]; 1.19 x 10-3 M in acetate buffers. Ordinate:

optical density, pH: (1) 4-29 and 4"64; (2) 3"96 and 4.91; (3) 3.78; (4) 3.51; (5) 3.30;
(6) 2.90.
DISCUSSION

The effective diameter estimated for the anions in solution is only a little greater
than that of the bare anion (I 1-2-11.5 A) which approximates to a sphere. Evidently
the hetero-9-molybdate ions, with a -6 charge but a low surface charge density, are
only slightly solvated, as are the 6-molybdocobaltatd TM and 12-tungstosilicatet18~ions.
The results of fused-hydrate cryoscopy, the spectral measurements, and the pH
titrations together show that the complexes are stable at 0-1-0.01 M concentration in
saturated Na~SO~ solution (although SO4*- ion is very slightly basic); but that some
decomposition occurs in more dilute solution. We regard deviations from Beer's law
as arising from attack by solvent, rather than from ion-pairing, as salts of other
highly-charged heteropolyanions (e.g. [CoW12040]6-) obey Beer's law accurately. It
is unfortunate that the immediate products of hydrolysis cannot be identified. It
appears that the Ni (IV) complex, although more easily reduced, is more resistant to
base hydrolysis than is the Mn complex. The latter is also decomposed in strongly
acidic solution; 9-molybdomanganic acid always undergoes some decomposition
during its preparation, with the formation of species which decompose directly to
MnO2 as the pH is raised so that the [MnMogOa2]~- ion cannot be reformed
quantitatively.

454

L . C . W . BAKERand T. J. R. WF_AKLEY

The spectra of Ni (IV) complexes have been little studied, and more data are
required for purposes of comparison before transitions can be identified with confidence. The absorption band at 17,600 cm-1 in the 9-molybdonickelate spectrum
(Fig. 5) probably arises from the transition 1Alg to 1T2g.
The spectrum of the 9-molybdomanganate ion requires some comment. The
maximum at 21,300 cm-1 (Fig. 4) has been assigned is) to the first spin-allowed transition
for a d a ion in octahedral co-ordination, 4A2gto ~T2g. The maximum at 25,500-26,000
cm-1 may be the second spin-allowed band, excited state 4T1~ (F). If this is so, then
a value of 370-420 cm-1 is obtained for the Racah parameter B, using the expressions
quoted by JORGENSElq(19) for the energies of the spin-allowed transitions. The "nephelauxelic ratio" fl is then 0.38 to 0.43 implying considerable covalency. The peak at
20,600 cm-1 has not yet been assigned. The Tanabe-Sugano diagram for d 3 suggests
that it is the transition to 2T~g (which is within the configuration t2~, and should
therefore give rise to a narrow band); but in that case, the means by which the
spin-forbidden transition gains intensity is not obvious. The transitions to 2Eg and
~T~g at 14,300 and 15,100 cm-1 are very much weaker. The latter transitions appear
very weakly at 14,500 and 14,900 cm-1 in the spectrum of 6-molybdochromate (III)
ion, 129) but no subsidiary peak is seen near the 4T2~ band; this anion is also based
on a MO6 group. It is therefore possible that the split peak at 21,000 cm-~ in the
spectrum of 9-molybdomanganate results from the appreciable distortion of the MnOe
group about the three-fold axis of the anion, which is indicated by the structural
data. (5) Crystals of the ammonium hetero-9-molybdates are strongly dichroic, with
colour changes from yellow to orange (Mn) and from red to almost black (Ni);
maximum absorption occurs when the electric vector has a large component along the
three-fold crystal axis. Polarized spectra at low temperatures should be informative.
The extinction coefficients for the spin-allowed bands of lowest frequency are 360
and 900 for the manganese and nickel complexes respectively. Even the spin-forbidden band at 14,300 cm-~ in the spectrum of the manganate has an extinction coefficient of about three. The nephelauxetic ratio, above, indicates that in the ground
state the metal d-electrons are considerably delocalized and are partly concentrated
on the polymolybdate "ligand"; we therefore suggest that the high intensities arise
because the electronic transitions are not pure d-d ones but involve some charge
transfer (from ligand to metal).
The failure to resolve the complexes and obtain ORD curves is disappointing, but
may result from the fact that the large anions, though their point symmetry is Da,
are nearly spherical (as a ball model reveals); therefore the enantiomorphs may
interact very similarly with optically-active ions or adsorbents.
c1,~C. K. JORGENSEN,in Progress in Inorganic Chemistry, Vol. 4, p. 96. Interscienc, New York (1962).
tso~T. J. R. WEAKImY,Unpublished work (1965).