Polyhedron Vol. 6, No. 6, pp. 1337-1342, 1987 0277~5387/87 S3.00+.

00
Printed in Great Britain 0 1987 Pergamon Journals Ltd

PREFERENTIAL SOLVATION AND ASSISTED

SUBSTITUTION OF CHLOROPENTAAMMINECOBALT(III)
ION IN WATER-DIMETHYL SULFOXIDE MEDIA

W. L. REYNOLDS*
Chemistry Department, University of Minnesota, Minneapolis, MN 55455, U.S.A.

and

MIRA GLAVAS and YU WAN

Chemistry Department, University of Sarajevo, Sarajevo, Yugoslavia

(Received 21 October 1986; accepted 17 November 1986)

Ahstrait-The composition of the solvent cage of chloropentaamminechromium(II1) ion

was determined in water-dimethyl sulfoxide media using proton NMR line-broadening
methods and the approach of Covington and coworkers. The number of solvent molecules
in the solvent cage was found to be 10. The stepwise formation constants for the substitution
of 10 water molecules by 10 dimethylsulfoxide molecules in this solvent cage were calculated.
After the first such substitution each successive substitution becomes 1027 J mol- ’ more
difficult, exclusive of statistical factors, than the preceding substitution. The solvent cage
composition was assumed to apply to the chloropentaamminecobalt(II1) ion. Mercury(II)-
assisted removal of chloride ion from the latter complex gave [Co(NH3),{OSMe2)13+/
[Co(NH3),(H20)13’ product ratios which did not correlate with either the solvent cage
composition or the activity ratio of the two solvent components in the bulk phase of the
solvent.

The solvent cage of a metal complex ML, which a stepwise formation constant given by eqn (2) :
has a well-defined first coordination shell of ligands
MLp*W,-i+ IDi- 1+D
L occupying p coordination sites, may be thought
of as a more labile and less well-ordered second
coordination shell around the ion. The number, n,, &MLP.W,O_j~i+~, (1)
of solvent molecules in, and the composition of, the
[ML, * Wn,-iDdaw
solvent cage in binary solvent mixtures is known for
(2)
a few complexes but this information is important in KiD= [ML,* Wn,_i+ IDi_ l]aD’
the interpretation of the properties and reactions of
Reynolds et al. 2.3h&e applied this theory to proton
the complexes. The Covington’ theory provides a
magnetic resonance line broadenings measured
means of determining n, and the composition by
in water-dimethyl sulfoxide solutions of
treating the solvent cage as a coordination shell in
which substitution of one solvent by a second occurs [Cr(NHJdOSMe2)13+and [Cr(NH3),(H20)13+.
For the former complex ion n, = 10 and for the
in a stepwise manner, as shown in reaction (l), with
latter n, = 12. Values of the stepwise constants for
both complexes were also reported. The com-
positions of the solvent cages were quantiatively
*Author to whom correspondence should be addressed. and simply related to the first-order rate constants
1337
1338 W. L. REYNOLDS et al.
for solvent interchange in reaction (3) :
& [Co(NH3)5{0SMe2}]3+ +H*O. (3)
I
Frankel ef ~1.~had previously shown that Cr(II1)
and Co(II1) complexes with like first coordination
shells had like solvent cages within experimental
error.
Langford and coworkers5-” have determined
compositions of solvent cages of a number of
Cr(II1) and Co(II1) complexes by NMR techniques
and found that frequently the solvent cages were
considerably richer in one solvent component than
was the solution as a whole. The term “preferential
solvation” has been used in the literature to describe
this situation ; if no “preferential solvation” occurred
the fraction of the solvent cage sites occupied by a
solvent component would be the same as the mole
fraction X, of that component in the solution as a
whole. It would be more accurate when ascertaining
whether a solvent is preferentially solvating a com-
plex to compare the ratio n,/nz, where n, is the
number of solvent cages sites around a complex
occupied by component 1 and n2 is the number of
these sites occupied by component 2, with the ratio
a,/az of the activities of the two solvent
components. When there are large deviations from
Raoult’s law it may be that :
X tion from aqueous solution with concentrated
9>!!>l
a2 n2 X2
or that
5,nl<_i* X Solvent cage studies
a2 n2 X2
In the former case the solvent cage is richer in
component 1 than is the solution as a whole but not
as rich as it should be given the high activity of 1
relative to 2 ; in this case it is incorrect to regard the
complex as preferentially selecting component 1 to
occupy solvent cage sites. In the second case the
solvent cage is richer in component 2 than is the
solution as a whole but not as rich as it should be
given the high activity of 2 relative to 1; again it is
incorrect to regard the complex as preferentially
selecting component 2 for solvent cage sites. How-
ever there is frequently a lack of quantitative data
concerning the activities of components in solvent
mixtures and the only comparison which can be
made is of n&z* with respect to X1/X2.
The water (W)--dimethyl sulfoxide (D) mixture
exhibits very non-ideal behaviour. At X, < 0.3 the
activities, a,, of dimethyl sulfoxide show large nega-
tive deviations from ideal behavior and
aD/aw c X,/X, but nJnw > X,/X, for the solvent
cages of aquo- and (dimethyl sulfoxide)penta-
amminechromium(II1) ions. Also the mole ratio
(n&z,+) remained greater than the activity ratio
(aJaw) up to X, = 0.9. The complexes preferred
dimethyl sulfoxide in the solvent cage and, in effect,
extracted dimethyl sulfoxide from its low activity
state in the bulk solvent phase into the solvent
cage. This result is consistent with the view that
a complex ion has a second coordination shell in
which one ligand (dimethyl sulfoxide) can replace
another ligand (water).
Here we report on the solvation number and
the solvent cage composition of Cr(NH3)&12+ in
water-dimethyl sulfoxide solvents and compare
the results with the ratio of the products formed
from the Hg2+-assisted removal of Cl- from
Co(NH3)C12+ in the same media.
EXPERIMENTAL
Chemicals
Aquo-, ’ ’ (dimethyl sulfoxide)-l2 and chlo-
ropentaamminecobalt(III)‘3 perchlorates were pre-
pared by literature methods. Chloro- and bro-
mopentaamminechromium(II1) dihalides were syn-
thesized from [Cr(NH,),(OH,)](NO,), *NH4N03
by the method of Zinato et a1.14 The dihalides
were converted to the perchlorates by precipita-
HC104. All the other chemicals were reagent grade
and were used as supplied.
These studies were made as described in detail3
previously only [Cr(NH3),C1](C104), and
[Cr(NH3),Br](C104)2 were used in place of the cor-
responding aquo and dimethyl sulfoxide complexes.
Line widths were obtained by magnifying the lines
many times on a screen and then measuring the
screen image with a millimeter scale.
The viscosities of the solvent mixtures at 40°C
were used to correct the measured line broadenings
as previously described. 3 The viscosity-corrected
increases in line width were then used to calculate
the ratio nilnOfor solvent i from eqn (4) :
Av~ Ni
ni
-=GxN,i. (4)
n,
In eqn (4) ni is the number of molecules of solvent
i in a total of n, solvent molecules in a solvent cage,
Ni and Noi are the total number of molecules of
the same solvent in the solvent mixture and in the
 Preferential solvation and assisted substitution of chloropentaanuninecobalt(III) ion 1339

neat solvent, respectively, and AViand Avei are the
proton line broademngs (corrected for viscosity
effect) of solvent i in the mixture and in the neat
solvent, respectively. The ratio q/n, is the fraction
of the solvent cage sites occupied by solvent i.
Kinetic studies
A known amount of the halo complex (usually
0.150 mmol) was dissolved in a predetermined vol-
ume of waterdimethyl sulfoxide solvent mixture
of predetermined ionic strength thermostatted at
a desired temperature. An excess of concentrated
Hg(ClO& was added quickly by syringe and the
assisted removal of the halide ion allowed to go to
completion. The reaction mixture was treated as
described previously” and, as then, the reaction
mixture was analysed sometimes by chromato-
graphic separation of the aquo and dimethyl sul-
foxide complexes, and sometimes by spectro-
photometric methods. Only these two products
were formed in the studies reported here.
RESULTS AND DISCUSSION
The solvent cage of [Cr(NH 3)sX]2+
The fractions of the solvent cage sites occupied
by dimethyl sulfoxide (n&z,) and water (+/no) were
calculated from eqn (4) and are given in Table 1
along with the activities of dimethyl sulfoxide and
water, the activity ratio Y = aD/aw, and the excess
free energy of mixing (AG3.
The enthalpies of mixing and the excess entropies
of mixing water and dimethyl sulfoxide at 25 and
70°C measured by Kenttamaa and Lindberg16 are
nearly independent of temperature. Their averages
were used to calculate values of AGE at 40°C which
were then fit to eqn (5) used by Scott et al. ” by the
method of least squares :
AGE = RTX,X&ln lO)[A+B(2X,- 1)
+ C(2X, - 1)2] (5)
The values of A-C determined from the least-
squares fit were used to calculate AGE values for
the many solvent mixtures of interest ; a few of these
are listed in Table 1.
The activities of water and dimethyl sulfoxide at
0.001 mole fraction intervals were calculated from
the excess free energies given by eqn (5) and the
Duhem-Margules equation. The successive
approximations to the correct activities of the two
solvents at each mole fraction were repeated until
the activities were constant to 16 significant figures
to reduce accumulation of error. Previously3 the
successive approximations had been repeated until
constancy to 10 significant figures had been
achieved. Comparison of the Y values in Table 1
with those previously obtained3 shows that, with
the exception of X, = 0.1, the activity ratios were
changed by much less than 1% by the increased
rigour of the calculations. It cannot be stressed too
strongly that good values of this ratio are needed ;
Y varies by a factor (29.706/0.0176) = 1688 from
X, = 0.1 to X, = 0.9 and, when n, = 10, Y” can
range over a factor of 2 x 103’ and other powers of
Y over a lesser, but still large, range. Poor Y values

Table 1. Values of the activities of dimethyl sulfoxide (Q,) and water (a,), the activity ratio
Y = a,/+,, the excess free energy of mixing (AC?, the fractions of the solvent cage sites occupied
by dimethyl sulfoxide (n&i,) and water (n&q,), and the stepwise formation constants for replacing
water by dimethyl sulfoxide in the solvent cage of Cr(NH3)gC12f

0 0 1.0 0 0 0 1.oooo -
0.1 0.0154 0.8580 0.0176 - 144.0 0.2234 0.8093 33.4477
0.2 0.0590 0.6791 0.0869 - 232.9 0.3850 0.6193 29.1701
0.3 0.1395 0.5116 0.2726 - 278.8 0.5356 0.5315 24.0084
0.4 0.2506 0.3740 0.6701 -291.9 0.6871 0.4236 24.87125
0.5 0.3784 0.2674 1.4149 -280.3 0.7883 0.2922 30.1622,
0.6 0.5103 0.1857 2.7474 - 250.3 0.8501 0.1972 33.9287
0.7 0.6401 0.1219 5.2516 - 206.0 0.9404 0.1481 31.71295
0.8 0.7663 0.0707 10.840 - 149.6 1.0345 . 0.0991 30.0375
0.9 0.8878 0.0299 29.706 -81.5 0.9682 0.0406 29.3718
1.0 1.0 0 - 0 1.oooo 0 -

‘Mole fraction of dimethyl sulfoxide based on solvents only.

b For n, = 10, k = 0.66092.
1340
would make it impossible to fit the experimental
data with one value of K’ in eqn (6) over the whole
solvent composition range. In eqn (6) the powers of
Y appear as coefficients in terms involving K’, the
first stepwise equilibrium constant for i = 1 in eqn
(2) with the statistical factor removed, and k, a
constant related to the incremental free energy
increase in the stepwise substitutions. Equation (6)
relates chemical-shift or line-broadening data to the
solvent cage parameters n,, K’ and k. The final
equation derived by Covington and Thain [eqn
(6) in Ref. l] contains a typographical error; the
power of k should read i(i-n)/2, not
(i(i- 1)/2) - ((n - 1)/2) (the expression given). ’
When the correct power of k is used the equation
is readily converted to a more convenient form,
namely :
I=
“0
(no!
soj
I+ ig, (n, _ i)!i! Y’Wki”- I)‘*
Here S,jS, = nj/noj for solvent j.
The solvent cage parameters in eqn (6) are fitted
to the nj/n,,j ratios obtained from line-broadening
data in the following manner. It is assumed that n,,
K’ and k are constant over the whole range of
solvent compositions. For a given solvent com-
position the value of Y is inserted into eqn (6) for
(say) dimethyl sulfoxide and an equation of the
form given in eqn (7a) is obtained :
nD A'
-=- or
no B ports the assumption that n, is constant over the
where A = n,A’/nD. For the other solvent com-
ponent (say water) there is an analogous equation
related to n&z, and insertion of the Y value gives
an equation of the form :
nw C’
-=- or l=o,
n, D eqn (2). For dimethyl sulfoxide replacing water
where C = n,C’lnw For a given value of n, the
denominators B and D are, and must be, equal.
Therefore A = C or, as given in eqn (8) :
A-C=O.
For a given n, and solvent composition there are an
infinite number of sets of (k, K’) values which will
satisfy eqn (8). Most of these sets do not remotely
satisfy eqn (8) when applied to other compositions
with other Y values ; the large range in the values
of the Yi coefficients can rapidly make A- C
unequal to zero when the (k, K’) set of values does
not fit that solvent composition. One (k, K’) set
should fit eqn (8) for all solvent compositions. How-
W. L. REYNOLDS et al.
ever, because of experimental error one (k, K’) set
will not be found which satisfies eqn (8) exactly for
all solvent compositions. Instead a (k, K’) set is
found which will minimize the sum of the squared
residuals given in eqn (9) for the solvent com-
positions studied :
C(Ai-Cl)* = 1~:. (9)
The smallest sum indicates the best fit of the par-
ameters (k,K’) for the assumed n,. The process is
repeated for other n, values until the best set of (n,,
k, K’) values giving the best fit is found.
For 40°C the ambient temperature at which the
NMR spectra were taken, the best set of values
was :
n, = 10, k = 0.66092, K’ = 29.8931.
When k = 0.66092 was used in eqn (8) for n, = 10
and eqn (8) solved for the value of K’ for each of
nine solutions the K’ values given in Table 1 were
obtained. The average value of K’ and the standard
deviation for determination of K’ from a single
(6) solution are 29.6+ 3.4. Thus the standard devi-
ation in the solvent range 0.1 < KD < 0.9 is
11.5%, which is very good considering the very
large range covered by the coefficients of k
and K’ in eqn (6). From Table 1 it is seen that
there is no trend in the K’ values with change
of solvent composition; this result supports the
assumption that n, and k do not change sig-
nificantly over the solvent range studied.
It can also be seen from Table 1 that the sum of
n&r, and n w/n, is unity or slightly greater, but does
(W not indicate any significant trend. This result sup-
solvent range studied. The tendency for the sum to
be somewhat greater than unity may result from
the viscosity corrections but the deviation is not
serious.
The k and K’ values obtained can be used’ to
C
(7b) give the stepwise equilibrium constants defined in
these are: K,, = 296, KD2 = 88.1, KD3 = 34.5,
KD4 = 15.0, KD, = 6.79, KD6 = 3.11, KD7 = 1.4,
K,, = 0.612, K,, = 0.240, and K,,,, = 0.0713.
The value k = 0.66092 means that on average it
(8) becomes more difficult by 1027 J mall ’ to replace
a water molecule by a dimethyl sulfoxide molecule
after each such substitution occurs.
It is seen from Table 1 that at KD = O.l(n,/n,) >
(x,/x,) > (a&w). Because a, <<K, the dimethyl
sulfoxide appears to be bonded in the bulk solvent
phase in a manner that greatly lowers its activity
from that expected on the basis of ideal behavior.
Despite this decrease in a, the mole ratio nD/nw for
the solvent cage is considerably greater than KD/xW
 Preferential solvation and assisted substitution of chloropentaamminecobalt(II1) ion 1341

and much greater then aJaw. We can conclude that Table 2. Percentages of [Co(NH3)SOSMe2]3+ (p,) and
Cr(NH3)&1*+ is strongly preferentially solvated by [Co(NH,),(H,O)]‘+ (pW) formed in the Hg*+-assisted
dimethyl sulfoxide. The data of Table 1 show that removal of Cl- and Br- from Co(NH3)a2+ in water-
nD/nw remains greater than a&, up to approxi- dimethyl sulfoxide solutions as functions of the mole
fraction (X,) of dimethyl sulfoxide : 2O.O”C < t < 6O.O”C
mately X, = 0.8 and that thereafter the ratio of the
solvents in the solvent cage approximately parallels
x- X, PD Pw PD/P W nD/nW
the activity ratio of the solvent in the bulk phase.
A few line-broadening measurements for Cl- 0.1 9.3f0.4 89.6kO.7 0.104 0.276
Cr(NH3)gBrZ+ at X, = 0.20,0.50 and 0.80 showed 0.2 14.3kO.3 84.3kO.6 0.169 0.622
that this complex closely paralleled the chloro com- 0.3 19.5,0X 78.7kO.8 0.247 1.01
plex in the composition of the solvent cage. The 0.4 28.8kO.6 69.3f0.7 0.416 1.62
studies were discontinued and it was concluded that 0.5 34.5f0.8 64.0f0.7 0.540 2.70
dimethyl sulfoxide preferentially solvated this 0.6 41.8f0.7 56.0f0.9 0.739 4.31
complex also at X, < 0.5. 0.7 49.6kO.7 48.8kO.6 1.02 6.35
The composition of the solvent cage of the chloro 0.8 56.710.8 42.0* 1.1 1.36 10.4
0.9 64.5kO.5 33.8kO.5 1.91 23.8
complex can be related to the solvent composition
Br- 0.1 9.6f0.4 88.4kl.l 0.108
X, by the following equation : 0.2 20.6f0.6 78.0f 1.2 0.265
0.3 30.5 +0.8 67.8 f0.5 0.450
0.4 39.9f0.8 58.6kO.9 0.680
0.5 50.0+ 1.1 49.0f 1.1 1.02
where C,, = -8.7646 x 10P6, C, = 1.79640, C2 = 0.6 60.0f0.9 38.7kO.7 1.55
17.3356, C3 = -209.2838, C4 = 1021.5398, Cs = 0.7 69.OkO.8 29.0f0.9 2.34
-2563.0867, C6 = 3451.8270, C, = -2368.6495, 0.8 79.0f0.7 2O.O-hO.7 3.93
0.9 87.7kO.8 10.6f0.6 8.24
and Cs = 649.5212. We are not aware that other
equations exist in the literature giving the com-
position of a solvent cage in terms of mole fractions
of solvents.
pentaamminecobalt(II1) complexes. The mech-
anism of the assisted substitution reactions of these
Hg2+-assisted substitution of Cr(NH3),XZ+ in complexes is less certain and a comparison of the
water-dimethyl sulfoxide solutions product ratios with solvent cage compositions is
desirable.
The Hg*+ -assisted release of X- (X- = Cl- or
The percentages of the dimethyl sulfoxide (pD)
Brr) from the first coordination shell of
and aquo (pw) complexes formed in reaction (10)
Co(NH&X2+ in water-dimethyl sulfoxide sol-
are given in Table 2 for 20, 40 and 60°C for the
utions leads to formation of CO(NH~)$~+
solvent range 0.1 < X, < 0.9 for X- = Cl- or Br-.
(S = water or dimethyl sulfoxide) as in reaction
The percentages listed in Table 2 were determined
(10):
4 times each at each of the three temperatures at
Co(NH&X2+ +Hg2+ + S each solvent composition. The percentage of each
product at each solvent composition remained the
+ Co(NH&S3+ +HgX+. (10)
same within the experimental error of less than 3%
It was of interest in the mechanism of substitution in the 2&6O”C temperature range so that only the
of S for X- to determine whether the product average and the standard deviation for a single
ratio [Co(NH3)5{0SMe2}3+]/[Co(NH3)5(H20)]3+ determination are listed.
formed was the same as the nD/nw ratio in the sol- When the values of the product ratio pD/pw for
vent cage around the reactant halo complexes. [It Cl- in Table 2 are compared with the solvent cage
was assumed that the Cr(NH3)5X2+ and CO(NH~)~ ratios (nD/nw) in the last column of Table 2 it is
X2+ complexes have very similar solvent cages.] readily seen that the composition of the solvent cage
In the solvent interchange reaction (3) it has been of Co(NH3)&12+ does not determine the product
found3 that k, is strictly second-order in n&z,, and ratio of reaction (10). Likewise when the product
that k, is strictly first-order in n&z, where n&z, ratios for Cl- are compared with the corresponding
and n&, were for the aquo- and (dimethyl Y values in Table 1 it is readily seen that the solvent
sulfoxide)pentaamminechromium(III) complexes, activity ratio does not determine the product ratio.
respectively. This finding strongly supports the In A possible explanation of these results is that for-
mechanism I8 which has previously been assigned mation of a dinuclear complex such as (NH3)&o
to the unassisted thermal substitution reactions of ClHg4+ prior to the rate-determining loss of Cl-
1342 W. L. REYNOLDS
very markedly changes the composition of the sol-
vent cage or at least makes water more available
near the departing HgCl+ group. It is very unlikely
that the five-coordinate intermediate Co(NH&’
was formed in the major pathway of reaction (10).
Firstly, if it were formed and if it reacted in a first-
order step with the solvent in its solvent cage then
the product ratio pD/pw values would be expected
to parallel the nD/nw values. This is because the
chloro-, bromo-, aquo- and (dimethyl sulfoxide)
pentaamminechromium(II1) complexes are all
strongly preferentially solvated by dimethyl sul-
foxide, and it seems likely that the five-coordinate
pentaammine complex would be also if it existed.
Secondly, if Co(NH,)z+ were formed as an inter-
mediate which reacted in a second-order (but
pseudo first-order) step with the bulk solvent com-
ponents then the po/pw values would be expected to
parallel the Y values. This is because the rate of
formation of the dimethyl sulfoxide product would
be proportional to the product ~c~(Nu~):+ x a,, the
rate of formation of the aquo product would be
proportional to the product ~c~(Nu~):+ x a, and
the product ratio would be approximately propor-
tional to aJaw. But this proportionality was not
observed.
Likewise the product ratios for Br in Table 2
show that they are not determined by no/q+, or
a&+,. Again these results are readily explained by
a dinuclear complex as in the case of Cl- but not
by the formation of the five-coordinate intermediate
Co(NH,):+.
It is concluded that the results of the product
ratio and solvent cage studies furnish rather strong
evidence against the formation of Co(NH&+ as an
intermediate with a lifetime sufficiently long to equi-
librate its solvent cage and to undergo diffusional
et al.
collisions with the major solvent components in a
major pathway in reaction (10).
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