Reactions of octacyanomolybdate(V) and octacyanotungstate(V) with s 2 metal-ion reducing centers

Article abstract of DOI:10.1039/b402460p

The s² centers, Sn(II), Ge(II), and In(I) reduce Mo ^v(CN)₈^3- and W^v(CN)₈ ^3- quantitatively to the corresponding octacyanomolybdate(IV) and -tungstate(IV) anions. Reductions by In(I) proceed 10³-10 ⁵ times as rapidly as those by Sn(II) and Ge(II). All reactions are triggered by a single electron oxidation, yielding a much more reactive s ^I intermediate. Reductions by Sn(II) in chloride medium proceed predominantly through the SnCl₃- anion. The Ge(II)-W(CN) ₈^3- reaction is initiated by a slow unimolecular heterolysis of the Ge(II) center, yielding very nearly linear profiles when the reductant is in excess. The Royal Society of Chemistry 2004.

Full text of DOI:10.1039/b402460p

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F U L L P A P E R
Reactions of octacyanomolybdate(V) and octacyanotungstate(V)
with s2 metal-ion reducing centers†‡
Zhiyong Yang and Edwin S. Gould*
Department of Chemistry, Kent State University, Kent, Ohio 44242, USA
Received 17th February 2004, Accepted 21st April 2004
First published as an Advance Article on the web 18th May 2004
The s2 centers, Sn(II), Ge(II), and In(I) reduce MoV(CN)83− and WV(CN)83− quantitatively to the corresponding
octacyanomolybdate(IV) and -tungstate(IV) anions. Reductions by In(I) proceed 103–105 times as rapidly as those by
Sn(II) and Ge(II). All reactions are triggered by a single electron oxidation, yielding a much more reactive s1 intermediate.
Reductions by Sn(II) in chloride medium proceed predominantly through the SnCl3− anion. The Ge(II)–W(CN)83− reaction
is initiated by a slow unimolecular heterolysis of the Ge(II) center, yielding very nearly linear profiles when the reductant is
in excess.
The present study deals with the reactions of Sn(II), Ge(II), and
Introduction
3−
3−
In(I) with the 4d- and 5d-block species Mo(CN)8 and W(CN)8
.
The recent availability of the hydrated p0s2-ions, indium(I)2 and
germanium(II)3 in workable concentrations has facilitated the ex-
amination of reactions with these strongly reducing 2e− species in
solution.
Kinetic patterns indicate the predominance of le− transactions, but
the Ge(II)–W(CN)83− system exhibits unexpected peculiarities.
Experimental
Of particular interest are oxidizing systems featuring three or
more accessible states differing by one unit, for in such cases,
reductions may conceivably proceed by single electron acts, by
two-unit transactions (oxo- or halonium-transfer), or by combina-
tions of these.
Materials
All solutions were prepared from Millipore-Q system deionozed
water that had been boiled for two hours and then purged with pure
argon for two hours more to remove dissolved oxygen. Indium
metal, silver trifluoromethanesulfonate (silver triflate), germanium
dioxide, sodium molybdate dihydrate (Na2MoO4·2H2O), sodium
tungstate dihydrate (Na2WO4·2H2O), potassium cyanide, potassium
borohydride, cesium chloride, and tri-n-butylamine (all Aldrich
products) were used as received.
Among the 3d-block oxidants, reductions of Cr(VI) and Cr(IV) by
s2 centers mainly involve 2e− steps, yielding Cr(II),4
Cr(VI) + Sn(II) → Cr(IV) + Sn(IV)
Cr(IV) + Sn(II) → Cr(II) + Sn(IV)
(1)
(2)
Cesium octacyanomolybdate(V) (Cs3Mo(CN)8) and the corre-
sponding octacyano tungstate salt were prepared by the procedures
of Liepoldt and coworkers.7 Stock solutions of indium(I) triflate in
anhydrous acetonitrile,2 Sn(II) solutions in HCl/NaCl,8 and Ge(II)
solutions in HCl3 were prepared and standardized as described.
and there is evidence that reductions of VO2+ are triggered by for-
mation of V(III).5
V(V) + Ge(II) → V(III) + Ge(IV)
V(III) + V(V) → 2 V(IV) (rapid)
(3)
(4)
Stoichiometric studies. Stoichiometric studies were carried
out under argon with the oxidants in excess and were monitored at
405 nm (for MoV) or 357 nm (for WV). Measured deficient quanti-
ties of each reductant were added to a known excess of the oxidant,
and the decreases in absorbance were compared to those resulting
from an excess of the reductant.
In contrast, profiles for reductions of Mn(III) and Mn(III,IV) com-
plexes1 are consistent with reactions involving only le− steps:
Mn(IV) + Ge(II) → Mn(III) + Ge(III)
Mn(III) + Ge(III) → Mn(II) + Ge(IV)
(5)
(6)
Kinetic studies. All reactions were performed under argon in a
darkened room, for both Mo(CN)83− and W(CN)83− are sensitive to
light. Freshly prepared Mo(V) and W(V) solutions were used. Rates
were evaluated from measurements of absorbance decreases of the
oxidant, using a Shimadzu 1601 UV-visible spectrophotometer or a
Durrum-Gibson stopped-flow spectrophotometer interfaced with an
OLIS computer system. Temperatures were kept at 22.0 ± 0.5 °C.
Ionic strength was maintained with LiCl/HCl or NaClO4/HClO4.
Concentrations were most often adjusted so that no more than 10%
of the reagent in excess was consumed in a given run (pseudo-first
order conditions). For the very rapid reactions, second order condi-
tions were necessary, but the InI–Mo(CN)83− reaction was too rapid
to measure, even using stopped-flow (k ≥ 4 × 107 M−1 s−1 at 20 °C).
For the slower reactions giving exponential curves, profiles were
followed for at least five half-life periods, and rate constants were
evaluated by nonlinear least squares fittings to the relationship corre-
sponding to first-order decay. Only one of the slower systems yielded
curves which were distinctly non-exponential; the Ge(II)–W(V) reac-
tion, when carried out with the reductant in excess, gave nearly linear
The situation with oxidations by Co(III) is mixed. In(I)–Co(III) reac-
tions are generally initiated by oxidation to In(II).2
Co(III) + In(I) → Co(II) + In(II)
(7)
(8)
In(II) + Co(III) → Co(II) + In(III) (rapid)
but reductions of corrin-bound Co(III) (vitamin B12a derivatives) by
Sn(II) and Ge(II) almost certainly are launched by the 2e− conversion
to a Co(I) transient:6
(corrin)Co(III) + Ge(II) → (corrin)Co(I) + Ge(IV)
(9)
(corrin)Co(I) + (corrin)Co(III) → 2 (corrin)Co(II) (rapid) (10)
†Electron Transfer. Part 158.1
‡Electronic supplementary information (ESI) available: Tables S1–S4;
detailed kinetic data for redox reactions. See http://www.rsc.org/suppdata/
dt/b4/b402460p/
1 8 5 8
D a l t o n T r a n s . , 2 0 0 4 , 1 8 5 8 – 1 8 6 1
T h i s j o u r n a l i s © T h e R o y a l S o c i e t y o f C h e m i s t r y 2 0 0 4

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Table 1 Stoichiometry of the reactions of Mo(CN)83− and W(CN)83− with
Table 2 Rate constants pertaining to the reduction of W(CN)83− by Ge(II)a
s2 metal-ion reducing centersa
[GeII]/mM
[H+]/M
[Cl−]/M
103k1/s−1
104(k−1/k2)/M
Reductant
Oxidant
[ox]/[red]
0.45
0.90
1.30
1.80
0.45
0.45
0.45
0.45
0.45
0.45
0.45
0.45
0.45
0.45
1.0
1.0
1.0
1.0
0.50
0.60
0.70
0.80
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
0.30
0.40
0.50
0.60
0.70
0.80
7.1
7.4
7.3
6.8
7.0
7.0
6.9
7.0
68
48
25
17
14
1.05
1.03
1.06
1.23
1.10
1.27
1.25
1.17
0.27
0.39
0.57
0.60
0.90
0.87
3−
3−
3−
In(I)
bMo(CN)8
bMo(CN)8
bMo(CN)8
1.91 ± 0.02c
1.94 ± 0.01d
1.91 ± 0.01d
1.94 ± 0.02c
1.93 ± 0.01f
2.01 ± 0.02g
Ge(II)
Sn(II)
In(I)
Ge(II)
Sn(II)
3−
3−
3−
eW(CN)8
eW(CN)8
eW(CN)8
a Reactions were carried out at 22.0 ± 0.5 °C in a darkened room. Oxidants
were Cs3Mo(CN)8 and Cs3W(CN)8. b Measurements at 389 nm. c Reactions
in acetate buffer (pH 4.7). d Reactions in 1.0 M HCl. e Measurements at 357
nm. f Reactions in 0.40 M HCl. g Reactions in 0.50 M HCl.
1.0
10
a Parameters pertain to sequence (18)–(19) in text. Reactions were run at
22 °C;  = 1.0 M (HCl/NaCl); [WV] = 0.10 mM throughout. Values listed
are those giving optimum agreement between calculated and observed ab-
sorbances for duplicate runs. Extinction coefficients were 1850 M−1 cm−1 for
W(V) and 230 M−1 cm−1 for W(IV). Path length 2.00 cm.
traces (rates independent of [WV]) during the first 80% reaction, after
which the profiles became curved. Interpretation of such patterns is
described in the Results and Discussion sections.
Results
The monophasic kinetic profiles obtained in most instances, and the
close approach to 2:1 stoichiometry observed throughout (Table 1)
are consistent with two-step sequences initiated by single-electron
transfer from the reductant, followed by a more rapid (and kineti-
cally silent) oxidation of the s1 intermediate, e.g.
[MoV][GeII](ko + kH[H+]KCl[Cl−])
d[MoV]/dt =
(17)
1+ KCl[Cl−]
and kH = (1.5 ± 0.2) × 103 M−2 s−1. Much of the reaction utilizes a
path involving one extra Cl− and an extra H+, in addition to a minor
W(V) + In(I) → W(IV) + In(II)
W(V) + In(II) → W(IV) + In(III) (rapid)
2 W(V) + In(I) → 2 W(IV) + In(III)
(11)
(12)
route (ko) requiring neither. The modest anation constant, KCl
=
0.20 M−1, pertaining to attachment of an additional Cl− to the pre-
dominant Ge(II) center, is consistent with that recorded earlier.6
(11) + (12)
3−
Reductions with In(I). Rates for the very quick In(I)–W(CN)8
Reductions of Mo(CN)83− (Eo 0.76 V),9 monitored here via stopped-
flow are, not unexpectedly, several orders of magnitude more rapid
than those of W(CN)83− (Eo 0.54 V).9
reactions (Table S-4‡) were measured under second order condi-
tions.13 The bimolecular rate constant, (2.0 ± 0.1) × 105 M−1 s−1,
exhibited no acidity dependence within the range [H+] = 0.010–
0.50 M. For the still more rapid In(I)–Mo(V) reaction, only a lower
limit, 4 × 107 M−1 s−1 (22 °C,  = 0.50 M) could be obtained.
Reductions by Sn(II). Kinetic data for the Sn(II)–Mo(V) and
Sn(II)–W(V) reactions (Tables S-1 and S-2‡) point to modest [H+]-
dependences, and we must also take into account the partition of
Sn(II) into four ligation levels:10
The Ge(II)–W(V) reaction. Among the systems studied, only
Ge(II)–W(V) exhibited multicomponent curves. Deviations from
exponential decay were most marked with Ge(II) in excess (Fig.
1). In such a case, profiles were linear (independent of [oxidant])
during the initial 70–80% of reactions, before becoming distinctly
curved. Slopes in the linear portion are proportional to Ge(II) but
very nearly inversely proportional to [Cl−]2.
This behavior implies that activation during the early stages in-
volves only the reductant, with the involvement of the oxidant rapid
enough to be kinetically silent. Later, as W(V) becomes nearly con-
sumed, its participation is slow enough to enter the picture. The pat-
tern calls to mind the reaction of Ge(II) with the very rapid oxidant,
Sn2+ + Cl−  SnCl+ (K1 = 11.2)
Sn2+ + 2Cl−  SnCl2 (K2 = 32)
Sn2+ + 3Cl−  SnCl3− (K3 = 14)
(13)
(14)
(15)
Sn(II)–Mo(V) and Sn(II)–W(V) rates conform to expression (16)
[ox][SnII](k3 + k3H[H+])K3[Cl−]3
1+ K1[Cl−] + K2[Cl−]2 + K3[Cl−]3
−d[ox]/dt =
(16)
− 3
I3 , in which the rate of redox is determined by unimolecular het-
erolysis of the reductant to a more reactive (tricoordinate) interme-
diate (designated Ge(II)* (18); the latter then reacts with W(V) (19):
in which the denominator reflects the partition of Sn(II) into chloro
complexes. The numerator points to two reaction paths, both in-
k1
−
H
volving the trichloro reductant, SnCl3 , one of which (k3 [H+])
requires an extra unit of H+. Refinements of data in terms of (16)
yield rate constants in Tables S-1 and S-2.‡ Alternate sequences,
involving the lower complexes of Sn(II) as well, did not improve
the fit. Calculated and observed rates are compared in the right hand
columns of these tables.
GeII-OH2
Ge(II)* + H2O
(18)
→
←
k−1
Ge(II)* + W(V) k2 → Ge(III) + W(IV)
(19)
(20)
Ge(III) + W(V) k3 → W(IV) + Ge(IV) (rapid)
The Ge(II)–Mo(V) reaction. In a reversal of the selectivities
observed with vanadium(V),5 1,4-quinones,11 and corrin-bound
Expression of sequence (18)–(20) as a series of differential equa-
tions and numerical integration using an adaptation of the program
KINSIM,14 yielded calculated absorbance curves which were com-
pared to the observed kinetic profiles. Kinetic parameters giving
optimal agreement between calculated and observed curves for
various runs are listed in Table 2: The reaction of the Ge(III) inter-
mediate is taken to be much more rapid than the initiation step (18),
in common with reactions of s2-metal reducing centers with a large
3−
cobalt(III),6 Sn(II) reduces Mo(CN)8 about 10 times as rapidly
as does Ge(II) (under comparable conditions) despite the more
favorable reduction potential (−0.22 V)12 assigned to the latter.
Reductions by Ge(II) (Table S-3‡) are considerably less sensitive
to changes in medium than those by Sn(II). The resulting rate law is
(17), refinement of which yields ko = (2.0 ± 0.2) × 102 M−1 s−1,
D a l t o n T r a n s . , 2 0 0 4 , 1 8 5 8 – 1 8 6 1
1 8 5 9

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Table 3 Rate laws and kinetic parameters for redox reactions of Mo(CN)83− and W(CN)83− with s2 metal-ion reducing centersa
Oxidation
Reduction
Rate laws
Parameters
W(V)
Mo(V)
In(I)b
In(I)b
k[ox][red]
k = (2.0 ± 0.1) × 105 M−1 s−1
k > 4 × 107 M−1 s−1c
[ox][red] (k3 + k3H[H+])K3[Cl−]3
1+ K1[Cl−] + K2[Cl−]2 + K3[Cl−]3
W(V)
Sn(II)d
k3 = 4.8 ± 0.3 M−1 s−1; k3H = 4.5 ± 0.4 M−2 s−1
K1 = 11.2e, K2 = 32e, K3 = 14f
Mo(V)
Sn(II)d
k3 = (1.71 ± 0.04) × 104 M−1 s−1
k3H = (3.5 ± 0.5) × 103 M−2 s−1
K1 = 11.2e, K2 = 32e, K3 = 14f
[ox][red](ko + kH[H+])KCl[Cl−]
1+ KCl[Cl−]
Mo(V)
W(V)
Ge(II)g
Ge(II)g
ko = (2.0 ± 0.2) × 102 M−1 s−1
kH = (1.5 ± 0.2) × 103 M−2 s−1; KCl = 0.2h
Sequence (18)–(20) in text
a Reactions were carried out at 22.0 ± 0.5 °C;  = 389 nm (for Mo), 357 nm (for W). b [H+] = 0.01–0.10 M; [CH3CN] = 0.005–0.50 M;  = 0.50 M (ClO4−).
−
c Reaction assumed to be first order in both redox partners. d [H+] = 0.10 = 1.0 M;  = 1.0 M (Cl−/ClO4 ). e Ref. 10. f Ref. 8. g [H+] = 0.2–1.0 M;  = 1.0 M
(HCl/Cl−) or (HClO4/ClO4−). h Ref. 6.
termediate; such a sequence is preferred for a large number of reduc-
tions of Co(III), Fe(III), and Ru(III) derivatives by In(I) and Ge(II);2,3,17
(B) Reactions of W(CN)83− are slower, by several orders of magni-
tude than those of the more strongly oxidizing Mo(V) analog.
The substitution-inert character of the cyano-bound oxidants and
the reluctance of the s2 reducing centers to utilize cyano bridges lead
us to assign outer-sphere paths to the reactions at hand. The 220 mV
Eo difference in formal potentials of the oxidants9 corresponds, in
terms of the Marcus model for outer-sphere process,18 to a 102-fold
difference in rate constants, in reasonable agreement to the ratios
observed.
The [Cl−]3-dependencies here noted for our Sn(II) reactions bring
to mind those found in an impressive variety of Sn(II) systems,
including reductions of vanadium(V),5 corrin-bound-cobalt(III),6
1,4-quinones,11 and the nitrosodisulfonate anion.19 In each of these
cases, the mechanistic burden is carried predominantly by the
SnCl3− anion. If the reaction involves separate le− transactions,11,19
Fig. 1 Kinetic profile at 357 nm for the reduction of W(V) (1.0 × 10−4
M) by Ge(II) (9.0 × 10−4 M) in 1.0 M HCl aqueous solution at 22 °C. The
solid line represents the experimental data obtained on stopped-flow reactor
whereas the solid circles were absorbances obtained by KINSIM integration
(ref. 14) based on sequence (18)–(19), taking k1 = 7.4 × 10−3 M−1 s−1, and
k−1/k2 1.04 × 10−4 M. Extinction coefficients were 1850 M−1cm−1 for W(V)
and 230 M−1 cm−1 for W(IV). Other species were considered to be negligibly
absorbent. Optical path length 2.00 cm.
attachment of extra chlorides to Sn(II) would be expected to alter
its ligand sheath to one resembling that of Sn(III), thus lowering
the Franck–Condon barrier to the transfer between states. If we are
dealing with a 2e− process,5,6 the effect of polyanation may reason-
ably be attributed to coulombic stabilization of the highly positive
Sn(IV) product.
The reversal of selectivity displayed by Mo(CN)83−, which re-
acts more rapidly with Sn(II) than with the more strongly reducing
state, Ge(II), is perhaps unexpected. It serves to remind us of the
reluctance of the latter reagent to undergo single electron oxida-
tion, implying a relatively high value (probably approaching 0.0 V)
number of le− oxidants.2,3 Note that this treatment allows us to esti-
mate the ratio k2/k−1, but not individual values of these parameters.
Although the rate constants resulting from this treatment cannot
be as precise as those obtained from single component curves, it is
evident that neither k1 nor the ratio k−1/k2 varies substantially with
[H+], but k1 is very nearly inversely proportional to 1/[Cl−]2. The
implication here is that the formation of the reactive intermediate,
Ge(II)*, is preceded by a rapid equilibrium involving loss of two
chloride ions from the principal Ge(II) species. Earlier experiments
by Poshkozim and Stone15 have indicated the latter to be GeCl42− in
0.1–0.5 M HCl.
−
2−
for Eo(GeIII/II). When the oxidant offers a 2e− path (e.g. I3 , PtCl6
)
allowing the donor to bypass GeIII, the potentiometrically-related
selectivity prevails, and reductions by GeII substantially outpace
those by Sn(II).
Undoubtedly, the most notable feature in the present study is the
3−
nearly linear profiles of the Ge(II)–W(CN)8 reactions generated
with the reductant in excess. The implication, that rates are deter-
mined by a process involving the reductant, but not the oxidant, is
closely related to that drawn for the Ge(II)–I3− reaction,3 and must
likewise be regarded as exceptional in that it runs counter to the
accepted view20 that slow metal–ligand bond breakage in coordina-
tion compounds in solution occurs only when activation requires a
significant loss in ligand field stabilization.
In contrast to the W(V)–Sn(II) reaction, which is markedly fa-
cilitated by addition by external chloride, the 1/[Cl−]2-dependence
associated with the initiation of the W(V)–Ge(II) reaction is reflected
in inhibition by chloride. Note that a chloride-influenced electron
transfer act is not involved in the rate-determining step in this case.
In summary, our experiments indicate that all but one of the oxi-
dations of our s2 centers are two-step processes triggered by slow
formation of an s1 intermediate. Points of special interest are: (A)
the unusual reactivity of the SnCl3− anion; and (B) the initiation of
2H2O
slow
2−
→
GeCl4
GeCl (H O) → Ge(II)* (21)
2 2 2
←
Thus, in this instance, the activation of Ge(II) entails two pro-
cesses; the loss of 2Cl− must be rapid and reversible to account for
the [Cl−]−2-dependency, but there must be an additional slow step
to accommodate the approach to linearity observed early in the
progress of the reaction.
Discussion
Rate laws and kinetic parameters are summarized in Table 3. Two
facets of this study may be considered unremarkable: (A) The stoi-
chiometries and kinetic profiles are, with a single exception, consis-
tent with oxidations of s2 species initiated by a le− act, followed by
a much more rapid transfer from the more strongly reducing16 s1 in-
1 8 6 0
D a l t o n T r a n s . , 2 0 0 4 , 1 8 5 8 – 1 8 6 1

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8 Z. Yang and E. S. Gould, J. Chem. Soc., Dalton Trans., 2002, 3840.
9 C. R. Dennis, A. J. Van Wyk, S. S. Basson and J. G. Leipoldt, Inorg.
Chem., 1987, 26, 270.
the Ge(II)–W(V) reaction by the slow unimolecular heterolysis of
the reductant.
10 R. M. Smith and A. E. Martell, Critical Stability Constants, Plenum,
New York, 1976, vol. 4, p. 109.
11 Z. Yang and E. S. Gould, Dalton Trans., 2003, 2119.
12 A. J. Bard, R. Parsons and J. Jordan, Standard Potentials in Aqueous
Solution, Marcel Dekker, New York, 1985, p. 212.
13 See, for example, J. H. Espenson, Chemical Kinetics and Reaction
Mechanisms, McGraw-Hill, New York, 2nd edn., 1995, p. 21.
14 B. A. Barshop, R. F. Wrenn and C. Frieden, Anal. Biochem., 1983,
130, 134.
Acknowledgements
We are grateful to the National Science Foundation for support of
this work, to Dr Olga Babich for valuable discussions, and to Mrs
Arla Dee McPherson for technical assistance.
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D a l t o n T r a n s . , 2 0 0 4 , 1 8 5 8 – 1 8 6 1
1 8 6 1