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Thermal properties of potassium bis(oxalato)diaquochromates(III) in solid

state. Trans–cis isomerization of the [Cr(C2O4)2(OH2)2]− complex ion in
aqueous solutions

Article in Structural Chemistry · April 2011

DOI: 10.1007/s11224-011-9876-y

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Struct Chem (2012) 23:333–340
DOI 10.1007/s11224-011-9876-y
ORIGINAL RESEARCH
Thermal properties of potassium
bis(oxalato)diaquochromates(III) in solid state. Trans–cis
isomerization of the [Cr(C2O4)2(OH2)2]2 complex ion
in aqueous solutions
Dagmara Jacewicz • Dariusz Wyrzykowski •
_
Krzysztof Zamojć • Diana Czerwińska •
Paulina Czaja Lech Chmurzyński
•
Received: 7 April 2011 / Accepted: 29 August 2011 / Published online: 14 September 2011
Ó Springer Science+Business Media, LLC 2011
Abstract The thermal decomposition of trans-
K[Cr(C2O4)2(OH2)2]3H2O and cis-K[Cr(C2O4)2(OH2)2]
has been studied using the TG–MS technique. The mea-
surements were carried out in an argon atmosphere over
the temperature range of 293–873 K. The influence of the
complex structures and configurational geometry on the
stability of the transition products and the pathways of
thermal transformations has been discussed. Further-
more, the kinetics of the isomerization reactions of the
[Cr(C2O4)2(OH2)2]- complex ion catalyzed by five dif-
ferent metal ions: Be2?, Mg2?, Ca2?, Sr2? and Ba2? have
been studied. The isomerization reactions were studied in
aqueous solution at five various temperatures (283–303 K),
at constant concentration of metal ions (C = 0.1 M) and
the constant ionic strength of solution (Na?, NO3-)
I = 2.4 M. The rates of the isomerization reaction were
determined spectrophotometrically by monitoring of absor-
bance changes at 410 nm.
Keywords Chromium(III) complexes 
Isomerization reaction  Thermal decomposition
Introduction
Methods of thermal analysis such as TG, DTA or DSC are
widely used for studying the complex formation in solid
_
D. Jacewicz (&)  D. Wyrzykowski  K. Zamojć  pn denotes DL-1,2-propane-diamine) is heated, it loses the
D. Czerwińska  P. Czaja  L. Chmurzyński
Faculty of Chemistry, Department of General and Inorganic
Chemistry, University of Gdańsk, Sobieskiego 18/19,
80-952 Gdańsk, Poland
e-mail: dagmara@chem.univ.gda.pl
state [1], the kinetics and mechanism of the thermal
decomposition [2], as well as for working out new methods
of compound synthesis of desired properties [3]. During
heating, ligands are released from the coordination sphere
of metal that leads to reduction of the coordination number
of a complex (Eq. 1) [4]:
   
PtðNH3 Þ4 Cl2ðsÞ ! PtðNH3 Þ2 Cl2ðsÞ þ 2NH3ðgÞ ð1Þ
In other cases, an anion can replace the ligand from the
coordination sphere of the metal (Eqs. 2, 3) and the
coordination number is preserved [5]. When an anion is
replacing a volatile ligand such as water, this type of
reaction is known as a deaquation reaction:
   
CoðNH3 Þ5 H2 O Cl3ðsÞ ! CoðNH3 Þ5 Cl Cl2ðsÞ þ H2 OðgÞ
ð2Þ
   
CrðNH3 Þ5 H2 O Br3ðsÞ ! CrðNH3 Þ5 Br Br2ðsÞ þ H2 OðgÞ
ð3Þ
The dehydration of some complexes leads to the change
of geometrical coordination of the complex. As an
example, the trans $ cis transformation is observed
during heating of solid trans-[Co(NH3)4Cl2]IO32H2O
(Eq. 4) [6]:
 
trans- CoðNH3 Þ4 Cl2 IO3  2H2 OðsÞ
! cis- CoðNH3 Þ4 Cl2 IO3ðsÞ þ 2H2 OðgÞ : ð4Þ
A similar behaviour has been also found for chromium(III)
complexes. When solid trans-[CrCl2(pn)2]Cl1.5H2O (where
hydration water and simultaneously isomerizes to cis-
[CrCl2(pn)2]Cl [7]. On the other hand, solid-phase thermal
cis- to trans-isomerization is also possible. For example,
it takes place during heating of cis-[NiBr2(bezen)2] and
123
334
cis-[Ni(NO3)(bezen)2]NO3 (where bezen denotes 1-nenzyl-
1,2-ethanediamine) (Eqs. 5, 6) [8]:
   
cis- NiBr2 ðbezenÞ2 ! trans- NiBr2 ðbezenÞ2 ð5Þ
   
cis- NiðNO3 ÞðbezenÞ2 NO3 ! trans- NiðNO3 Þ2 ðbezenÞ2
ð6Þ
However, to the best of our knowledge, there are
no reports on thermal decomposition of trans-K[Cr(C2O4)2
(H2O)2]3H2O and cis-K[Cr(C2O4)2(H2O)2]. This was the
main reason that prompted us to perform the studies
described in this study.
Isomers of a given compound are commonly defined as
substances having the same stoichiometric composition,
the same molecular weight, and the same chemical for-
mula, but different structures which behave generally dif-
ferently with respect to most chemical and physical
properties. A complex which possesses the same two
ligands occupying adjacent positions is called the cis iso-
mer, while complex which possesses these ligands occu-
pying positions across from one another, or on opposite
sides in the octahedron, is called the trans isomer. Cis–
trans isomers are called geometrical isomers (or diaste-
reomers) [9–15].
There is a great interest in understanding the preference
of different transition metals for cis or trans isomers or the
way in which these complexes undergo geometrical
isomerization. Indeed, the course of many reactions of
these species, such as nucleophilic substitution, electron
transfer, oxidative addition, reductive elimination, thermal
decomposition or interaction with molecules of biological
interest is dictated by the geometry of these compounds
[9, 16–20].
The relative reactivity of cis–trans isomeric pairs is
related to their physical and chemical properties. Thus,
information concerning isomerization barriers is essential
for rational synthetic design and for understanding the
reactivity of the isomers.
Isomerization of transition metal complexes is fre-
quently observed to occur from octahedral d6 or square to
planar d8 systems. Although the interconversions between
isomers are commonly achieved thermally, they are also
induced photochemically (isomerization brought about by
irradiation with ultraviolet or sometimes visible light), by
the addition of a suitable catalyst or by oxidation/reduction.
In the latter case, the thermodynamically favoured isomeric
distribution depends on the oxidation states of the metal
centre of the complex [9, 10, 21–28].
The interconversion of the cis and trans isomers of
organic compounds has been known to chemists almost
ever since the discovery of geometrical isomerism. While
the cis and trans isomers of organic compounds containing
123
Struct Chem (2012) 23:333–340
isolated double bounds are usually stable and relatively
drastic conditions are required to cause isomerization, the
interconversion of the geometrical isomers of conjugated
compounds occurs more readily, and in the case of some
highly conjugated compounds precautions are necessary in
order to prevent isomerization. The application of new
physical techniques, particularly spectroscopy and chro-
matography, has permitted the study of the cis–trans
isomerization of conjugated molecules that had previously
gone unnoticed [10].
The thermal cis–trans isomerization of a number of
organic compounds has been already studied by kinetic
methods. The product of the reaction is always a more
stable isomer. A large amount of compounds of different
types have been found to catalyze the cis–trans isomeri-
zation reactions. The product of the catalytic isomerization
is also a more stable isomer. In contrast with the thermal
and catalytic isomerization, the photochemical reactions
tend to produce the less stable isomers [17, 22–24, 27].
In this study, the kinetics of isomerization reaction of
[Cr(C2O4)2(OH2)2]- complex ion catalyzed by Be2?,
Mg2?, Ca2?, Sr2? and Ba2? ions has been investigated.
The selection of chromium(III) as the centre of coordina-
tion permits to obtain inert complexes which undergo rel-
atively slow transformations at ambient temperature, thus
enabling to carry out investigations on the kinetics and
mechanism of the processes. Studies on the isomerization
reactions are very important since such processes often
occur in the biological conditions in living organisms, and
because the impact of physicochemical factors on isomer-
ization is not the same for the various transition elements
and their compounds [29–31].
Experimental section
Reagents
The cis- and trans-potassium bis(oxalato)diaquochro-
mates(III) were prepared by the methods of Werner [32]
as adapted by Palmer [33]. The purity of each salt was
checked by elemental analysis for C and H. The results
of analytical calculations for trans-K[Cr(C2O4)2(OH2)2]
3H2O: C, 13.66; H, 2.85; and for cis-K[Cr(C2O4)2(OH2)2]:
C, 15.91; H, 1.95; were in agreement with those of the
elemental analysis: C, 13.62.; H, 2.84 and C, 15.92.; H,
1.97, respectively.
IR spectra
The IR spectra were recorded on a BRUKER IFS 66
spectrophotometer in a KBr pellet.
Struct Chem (2012) 23:333–340 335

Thermal analysis

Thermal decomposition of trans-K[Cr(C2O4)2(OH2)2]3H2O

and cis-K[Cr(C2O4)2(OH2)2] has been studied using the TG–
MS technique. The TG–MS measurements in argon (Ar 5.0)
were run on a STA 449 F3 JupiterÒ thermal analyzer (Netzsch)
coupled with a QMS 403 C Ae¨olosÒ quadrupole mass spec-
trometer. The measurements were carried out in an argon
atmosphere over a temperature range of 293–873 K (Al cru-
cible with a small central hole, sample mass 5–10 mg, heating
rate 10 K min-1, flow rate of the carrier gas 20 mL min-1).

Kinetic measurements

The stock solutions containing cations used as catalysts

were prepared using the nitrate salts of the cations. Solu- Fig. 1 IR spectrum for the trans-K[Cr(C2O4)2(OH2)2]3H2O
tions containing all five cations studied were prepared by
mixing the proper volumes of the stock solutions of cations
(0.1 M) and sodium nitrate to bring the ionic strength to
2.4 M. Next, nitric acid was added to adjust the pH to
about 2 and finally the solution was diluted to desired
volume with deionized water. 2 mL of such solution was
placed in a cuvette, which was thermostated at the snap of
temperature control (Peltier system) with the option of
mixing and water circulation. Then, the solution was added
to the cuvette with pure, finely grounded complex, trans-
K[Cr(C2O4)2(OH2)2]3H2O, stirred until the dissolution of
the sample and subsequently the trans–cis isomerization
reaction of the complex studied was monitored spectro-
photometrically. The pH of about 2 was chosen because at
this value the hydrogen ion has no catalytic effect and at
the same time the hydrolysis of the cations used as catalysts
could be minimized. The rate of reactions studied was
measured at the wavelength equal to 410 nm by using the
Fig. 2 IR spectrum for the cis-K[Cr(C2O4)2(OH2)2
method of Guggenheid [34] as modified by King [35].

Instrumentation and simulations

Spectral measurements were carried out in the UV–Vis
region using a Perkin-Elmer Lambda 650 Instrument with
the scan accuracy of 1 nm and 1 nm slit width at a scan-
ning rate of 120.00 nm min-1. The observable rate con-
stants were computed using a ‘Glint’ program based on
global analysis [36–39].
Results and discussion
IR spectra
Differences in the structures of the obtained geometric
isomers cis and trans were confirmed on the basis of their
IR spectra. Figures 1 and 2 show the infrared spectra for
the trans-K[Cr(C2O4)2(OH2)2]3H2O and cis-K[Cr(C2O4)2
(OH2)2 complex salts, respectively. As observed, the spectrum
of the trans-K[Cr(C2O4)2(OH2)2]3H2O contains asymmetri-
cal stretching vibrations bands characteristic for C=O bond
with minima at 1709.8; 1690.6 and 1659.5 cm-1, whereas for
the cis form {cis-K[Cr(C2O4)2(OH2)2} these bands are shifted
to lower wavenumbers 1709.2, 1681.5 and 1615.5 cm-1,
respectively. Remaining bands are very similar for both iso-
mers. O–C=O bending the vibrations display band at
1265.5 cm-1 for cis and trans form. Both forms show bands of
medium intensity at about 1390 cm-1 coming out from C–O
and C–C stretching vibrations. Wide intensive bands at about
3000 cm-1 result from the vibrations of water in the coordi-
nation sphere of both complexes. Furthermore, for both
complexes at about 550 cm-1 there is the band characteristic
for Cr–O stretching vibrations [40].

123
336 Struct Chem (2012) 23:333–340

Thermal analysis
Results of thermal analysis of trans-K[Cr(C2O4)2
(OH2)2]3H2O and cis-K[Cr(C2O4)2(OH2)2] are collected in
Table 1. The TG curves of the compounds under study
recorded at a heating rate of 10 K min-1 are shown in
Fig. 3. As seen, trans-K[Cr(C2O4)2(OH2)2]3H2O and cis-
K[Cr(C2O4)2(OH2)2] exhibit comparable thermal stabilities
but their geometric configurations have a fundamental
influence on the course of their decomposition. Examination
of the ion currents and the TG curve has shown that during
the first step, the former isomer losses three molecules of
crystal water (m/z = 17, 18) to form trans-K[Cr(C2O4)2
(OH2)2] at ca. 391 K (Fig. 3). The dehydrated salt, trans-
K[Cr(C2O4)2(OH2)2], is stable in a relatively broad range of
temperature (391–478 K). In the second step (478–554 K),
the trans isomer losses two molecules of coordination water
to form K2C2O4 and Cr2(C2O4)3 at 554 K. At higher tem-
perature, K2C2O4 and Cr2(C2O4)3 undergo decomposition to
K2CO3 and Cr2O3, as well as the gaseous products are
released as CO (m/z = 28) and CO2 (m/z = 28, 44) (Fig. 4).
A similar behaviour has also been observed in the indium
analogue K[In(C2O4)2(OH2)2]3H2O [41].
The cis-K[Cr(C2O4)2(OH2)2] complex does not contain
crystal water. Similar to trans-K[Cr(C2O4)2(OH2)2]3H2O,
its decomposition starts at 343 K, but is connected with
losing two molecules of coordination water (m/z = 17, 18)
and leads to the formation of K2C2O4 and Cr2(C2O4)3
(Fig. 5).
The temperature of decomposition of cis-K[Cr(C2O4)2
(OH2)2] is much lower than that of the dehydrated trans-
K[Cr(C2O4)2(OH2)2] (Table 1). Moreover, the rate of losing
of coordinated water is ca. three times faster in the case of
the trans complex. In comparison, maximum mass loss rates
that correspond to the release of coordination water, deter-
mined from the DTG curves, at a heating rate of 10 K min-1
are 3.5%/min at 530 K and 1.2%/min at 419 K for trans and
cis isomer, respectively (Fig. 3). This finding indicates that

Table 1 Thermal decomposition data of trans-K[Cr(C2O4)2(OH2)2]3H2O and cis-K[Cr(C2O4)2(OH2)2] in argon

Complex salt Ranges of Mass loss% Intermediate and
decomposition (K) final solid products
Found Calcd.

trans-K[Cr(C2O4)2(OH2)2]3H2O 343–391 15.0 15.12 trans-K[Cr(C2O4)2(OH2)2]

478–554 10.7 10.1 K2C2O4, Cr2(C2O4)3
554–873 34.2 34.2 K2CO3, Cr2O3
cis-K[Cr(C2O4)2(OH2)2] 343–576 11.5 11.9 K2C2O4, Cr2(C2O4)3
576–873 37.3 40.3 K2CO3, Cr2O3

Fig. 3 TG curves of thermal

decomposition of trans-
K[Cr(C2O4)2(OH2)2]3H2O and
cis-K[Cr(C2O4)2(OH2)2] in
argon, b = 10 K min-1

123
Struct Chem (2012) 23:333–340 337

Fig. 4 Ionic current profiles

recorded during TG-MS
analysis of trans-
K[Cr(C2O4)2(OH2)2]3H2O
in argon, b = 10 K min-1

the trans configuration of the examined compound is more Kinetic studies

thermodynamically stable in solid than the cis one.
On the basis of the MS spectra of the volatile products of Schlafer et al. [42] have reported that the rate of the trans–
the decomposition of trans-K[Cr(C2O4)2(OH2)2]3H2O and cis isomerization is independent of added magnesium ion,
cis-K[Cr(C2O4)2(OH2)2] (Figs. 4, 5) as well as mass lost whereas Besse and Johnson [43] have stated that the
(TG curves) the following equations describing thermal racemization of tris(oxolato)chromate(III) is dependent
decomposition of the compounds studied can be suggested: upon a large number of different cations, including mag-
  nesium. A preliminary investigations in this laboratory
2 trans-K CrðC2 O4 Þ2 ðOH2 Þ2  3H2 O
  have shown that the kinetics of the isomerization reaction
343 K
! 2 trans-K CrðC2 O4 Þ2 ðOH2 Þ2 þ 6H2 O ð7Þ of the [Cr(C2O4)2(OH2)2]- complex ion depends on the
  478 K type of catalyst and temperature. Because of the discrep-
2 trans-K CrðC2 O4 Þ2 ðOH2 Þ2 ! K2 C2 O4 ancies of the findings on this system it was decided to
þ Cr2 ðC2 O4 Þ3 þ 4H2 O ð8Þ investigate the catalytic effect of several different metal
554 K ions, e.g. Be2?, Mg2?, Ca2?, Sr2? and Ba2? on the trans–
K2 C2 O4 þ Cr2 ðC2 O4 Þ3 ! K2 CO3 þ Cr2 O3 þ 3CO2 cis isomerization of bis(oxalato)diaquochromate(III) .
þ 4CO ð9Þ The isomerization reaction of [Cr(C2O4)2(OH2)2]-
complex ion can be presented as follows:
Summary:
  The progress of the isomerization reaction of
2 trans-K CrðC2 O4 Þ2 ðOH2 Þ2  3H2 O [Cr(C2O4)2(OH2)2]- complex ion catalyzed by five dif-
! K2 CO3 þ Cr2 O3 þ 3CO2 þ 4CO þ 10H2 O ð10Þ ferent metal ions was monitored spectrophotometrically.
  343 K Figure 6 shows the changes in the absorption of the
2 cis-K CrðC2 O4 Þ2 ðOH2 Þ2 ! K2 C2 O4 isomerization reaction of trans–cis-[Cr(C2O4)2(OH2)2]-
þ Cr2 ðC2 O4 Þ3 þ 4H2 O ð11Þ complex ion catalyzed by calcium ion. As seen on the
576 K electronic spectra (Fig. 6), the trans-/cis-[Cr(C2O4)2
K2 C2 O4 þ Cr2 ðC2 O4 Þ3 ! K2 CO3 þ Cr2 O3 þ 3CO2
(OH2)2]- complex ions have absorption maxima at almost
þ 4CO ð12Þ the same positions. However, the molar absorption coeffi-
Summary: cient of the cis isomer is much larger than for the trans
  isomer, and it allows the application of spectrophotometric
2 cis-K CrðC2 O4 Þ2 ðOH2 Þ2 ! K2 CO3 þ Cr2 O3 þ 3CO2 technique in the investigations of the kinetics of the
þ 4CO þ 4H2 O ð13Þ isomerization reaction (Scheme 1).

123
338
Fig. 5 Ionic current profiles
recorded during TG-MS
analysis of cis-
K[Cr(C2O4)2(OH2)2] in argon,
b = 10 K min-1
Carrying out the spectrophotometric measurements of
isomerization reaction of the trans-[Cr(C2O4)2(OH2)2]-
complex ion catalyzed by five different metal ions of the
second group of the periodic table, it is possible to note that
for all probes the approximated curves decay monoexpo-
nentially and the reaction studied proceeds in one step.
A linear function of ln(A? - A) versus time (t) (Fig. 7)
is consistent with the following kinetic equation:
 
d trans- CrðC2 O4 Þ2 ðOH2 Þ2 =dt
¼ k trans- CrðC2 O4 Þ2 ðOH2 Þ2 ð14Þ
In order to determine the values of rate constants
two methods, namely the singular value decomposition
Fig. 6 Absorbance changes for the isomerization reaction of trans–
cis-[Cr(C2O4)2(OH2)2]- complex ion ([Ca2?] = 0.1 M, T = 298 K,
pH = 2, I = 2.4 M)
123
Struct Chem (2012) 23:333–340
analysis (SVD) and global analysis (GA) based on model
of reaction A ? B were used. It should be highlighted
that using both methods the same results were obtained.
The rate constants for the isomerization reaction of trans-/
cis-[Cr(C2O4)2(OH2)2]- complex ion catalyzed by five
different metal ions are compiled in Table 2.
Based on the kinetic data obtained, the dissociation
mechanism for the studied coordination ion has been pro-
posed (Scheme 2).
The values of the rate constants of isomerization
reaction for this complex can be compared with the lit-
erature data available for ligand exchange in the trans-
[Cr(C2O4)2(OH2)2]- complex ion [44]. It turned out that
the rate of the isomerization is 120 times faster than
aquo ligand exchange and 2700 times faster than oxolato
anion ligand exchange. On this basis, it can be stated
that the reaction of isomerization of this complex ion
proceeds according to the dissociative mechanism. In
the first step, the slow dissociation in the trans-
[Cr(C2O4)2(OH2)2]- ion takes place during which a bond
between chromium and oxygen atom from the oxolato
anion is broken (Scheme 2a, b). This bond is reconsti-
tuted on the other side of coordination center. Next, the
bond between chromium ion and oxygen atom from
the second oxolato anion is broken and, consequently,
the complex ion of the structure of trigonal bipyramid
in which chromium (III) ion is five-coordinated
(Scheme 2c) is formed. Sequentially, the bond between
chromium ion and oxygen atom from oxolato anion is
reconstituted and the cis-[Cr(C2O4)2(OH2)2]- complex
ion is formed (Scheme 2d).
Struct Chem (2012) 23:333–340 339

Scheme 1 The isomerization reaction of trans-/cis-[Cr(C2O4)2(OH2)2]- complex ion

properties complex salts under study have been investi-

Fig. 7 The linear function of ln(A? - A) versus time (t) for the
isomerization reaction of [Cr(C2O4)2(OH2)2]- complex ion catalyzed
by calcium ion
Conclusions
For trans-K[Cr(C2O4)2(OH2)2]3H2O and cis-K[Cr(C2O4)2
(OH2)2] complex salts, IR spectra were recorded to confirm
differences in their structures. Subsequently, the thermal
gated in a neutral atmosphere (Ar). The TG–MS analysis
has shown that the configurational geometry affects the
thermal stability of the compounds studied. The studies
reveal that in the solid state the trans-isomer is thermo-
dynamically more stable than the cis-isomer. The analysis
of the MS spectra shows that both compounds studied
undergo dehydration and decarboxylation leading to the
formation of K2CO3 and Cr2O3. On the basis of TG–MS
data, the equations of thermal decomposition of the trans-
K[Cr(C2O4)2(OH2)2]3H2O and cis-K[Cr(C2O4)2(OH2)2]
complex salts have been proposed. Furthermore, the
kinetics of isomerization reaction of [Cr(C2O4)2(OH2)2]-
complex ion catalyzed by five different metal ions (Be2?,
Mg2?, Ca2?, Sr2?, Ba2?) was studied. A mechanism of
isomerization reaction of [Cr(C2O4)2(OH2)2]- complex ion
has been proposed on the basis of the kinetic data. It
assumes that the isomerization reaction proceeds in a single
step according to the dissociative mechanism. Moreover,
on the basis of results obtained it has been found that the
reaction rate of isomerization only slightly depends on the
type of ion used as catalyst. On the other hand, the tem-
perature dependence shows that with the increasing tem-
perature the reaction rate of isomerization increases.

Table 2 The rate constants for the isomerization reaction of trans–cis-[Cr(C2O4)2(OH2)2]- complex ion (Cmetal ions = 0.1 M, pH = 2, ionic
strength 2.4 M)
Metal Temperature (K)
ion
283 288 293 298 303
2? -4 -4 -4 -4
Be 1.49 9 10 2.51 9 10 4.30 9 10 7.53 9 10 12.20 9 10-4
(±0.01 9 10-4) (±0.02 9 10-4) (±0.03 9 10-4) (±0.07 9 10-4) (±0.10 9 10-4)
Mg2? 1.43 9 10-4 2.35 9 10-4 4.42 9 10-4 8.03 9 10-4 11.10 9 10-4
(±0.01 9 10-4) (±0.01 9 10-4) (±0.03 9 10-4) (±0.07 9 10-4) (±0.10 9 10-4)
Ca2? 1.75 9 10-4 3.05 9 10-4 5.89 9 10-4 9.18 9 10-4 14.30 9 10-4
(±0.01 9 10-4) (±0.01 9 10-4) (±0.06 9 10-4) (±0.01 9 10-4) (±0.10 9 10-4)
Sr2? 1.64 9 10-4 2.77 9 10-4 5.14 9 10-4 8.14 9 10-4 13.90 9 10-4
(±0.01 9 10-4) (±0.02 9 10-4) (±0.05 9 10-4) (±0.07 9 10-4) (±0.20 9 10-4)
Ba2? 1.70 9 10-4 2.69 9 10-4 4.87 9 10-4 7.99 9 10-4 14.00 9 10-4
(±0.01 9 10-4) (±0.01 9 10-4) (±0.05 9 10-4) (±0.07 9 10-4) (±0.20 9 10-4)

123
340
Scheme 2 The proposed mechanism of the trans–cis isomerization
of [Cr(C2O4)2(OH2)2]- ion
Acknowledgements This study was financially supported by Polish
Ministry of Science and Higher Education under grants N N204
132040 and DS/8232-4-0088-1.
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