The Lability Of Water Exchange rate Of Trans- bis(oxalato) diaquo

Chromate(III) Ion With Arginine By Trans-Effect Of Internal Conjugated

Base Formation
M. A. Abdullah* , B. K. Aziz
Department of Chemistry, University of Sulaimani.

Abstract
The reaction of the trans- bis(oxalato) diaquo chromate (III) ion with amino acid arginine has
been studied at different temperatures and pH 4.8-5.7 in aqueous solution. The equilibrium constant
for this substitution reaction at 250C gives logKequ= 4.63. The kinetic interaction involves two parallel
reactions of three different subsequent steps of different Cr(III) species that gives only cis-mono(Arg-O,N) bis(oxalato) chromate(III) complex according to scheme below:
Trans-[Cr(ox) 2 (H 2 O)OH ] 2-+ArgO H

K'os

k1
Trans-Cr(ox)(H 2 O)OH,ArgOH

outer-sphere

k -1

Kh

(I 1 )

K os

k -2

(I 2 )

[cis-Cr(ox) 2 (ArgO)]2-

k -5

k6

k -3
k3

cis-[Cr(ox) 2 (ArgO)(H 2 O )] 2-

Trans-Cr(ox)(H 2 O) 2,ArgOH

outer-sphere

k -4
k

k2
Trans-[Cr(ox) 2 (H 2 O) 2 ] -+ArgOH

Trans-[Cr(ox) 2 (ArgO)OH ] 2-

Trans-[Cr(ox) 2 (ArgO)(H 2 O)] 2-

k -6

(I 3 )

( ArgO is amino acid Argininato ion, water molecules are omitted and I1, I2 and I3 are intermediate species)

The Ea for the internal water exchange reactions of formation I1, I2 and I3 of steps k1, k2 and
k3 are 6.14, 17.2 and 8.85 Kcal/mole, and the S values are -45.3, -20.36 and 49.3 eu
respectively. These data are consistent with interchange associative mechanism and fit to the
kinetically trans-effect labilization of water exchange rates of outer sphere complexes of internal
conjugated base formation by hydrogen bonding.

Introduction:
Slow ligand substitution rates of inert
Cr(III) (d3-configuration) are well known, the
rate constant of water-solvent exchange at
Cr(III) is ki=0.501X10-6 sec-1at 250C with
activation energy Ea =26.6 Kcal/mol. (1).
However, many reactions of water exchange
of Cr(III) with other ligands were recorded to
have higher rates and lower activation
parameters than water- solvent exchange in
aqueous solution. We have recently studied the
equilibrium, kinetic and mechanistic of
replacement two axial water molecules of
trans-[ Cr (C2O4)2(H2O)2]-2 with amino acids,
glycine, alanine and histidine in moderately
acid solution of pHs 4.8-6.7 (2). We found that
the observed rate of water exchange at
conjugated complex [Cr(C2O4)2(H2O)OH]-- is
much faster than that of diaquo complexes
[Cr(C2O4)2(H2O)2]-. The first rate constant of
conjugated base, under excess of amino acid
condition was found to follow the rate law:
kobs1 = k + k [H+]-1 and it is zero order on the
amino acid concentrations. While the second

rate is also zero order dependent on amino acid

ligands and independent of acid concentration.
The suggested mechanism was shown to
follow that of Eigen Willkenson mechanism
(3) with the distinctive outer-sphere complex
derived from trans-[Cr(C2O4)2(H2O)2]- and its
conjugated base, trans-[Cr(C2O4)2(H2O)OH]2-,
with incoming zweeter ion of amino acids in
solution.
Several similar studies of Cr(III) reactions
with amino acids were reported previously
(4,5),but there is no obvious reason why the
interchange rates of axial water with different
amino acid are faster in Cr(III) conjugated
base complexes, so we have studied the
reaction of arginine, amino acid polydentate
ligand which causes a kinetically trans- effect
via of high tendency to from hydrogen
bonding formation with reactants trans
[Cr(C2O4)2(H2O)2]2-complex
and
its
conjugated base. This paper reports the results
of this study.

Experiment:
All chemicals used in this study were all
reagents analytical grade, oxalic acid,
potassium hydrogen carbonate, and potassium
dichromate were obtained from Riedel De
Haen, Hanover, Sodium nitrate and arginine
were bought from BDH.All are used with out
further purification.
Jenway
66405
UV-Visible
spectrophotometer with locally modified
thermostat cell holder was used for measuring
absorbance
and
recording
electronic
absorption spectra A Buchi chromatographic
pump is used to circulate the sample solution
from thermostatted reaction vessel to the flow
cell. A Philips pH/mv meter PW 9414 type
was used for pH measurements. A circulating
thermostat bath (LKB Bromma 2209
multitemp.) was used to control temperature to
0.1oC.
Trans-K[Cr(C2O4)2(H2O)2].3H2O complex has
been prepared by following the Dawson
procedure (6). The obtained crystals have been
washed several time with cold water, alcohol
and dried, then dried sample was analyzed for
C,H,N,K and Cr before using.
Kinetic and thermodynamic studied were
performed by mixing thermostatted solutions
of arginine and Cr(III), and adjusting the pH to
the required valve pHs with NaOH ( or
HNO3). The thermostatted mixture was
circulated through the flow cell in the
thermostatted block of spectrophotometer at
the same temperature then the intensity
absorption change (Aobs) was recorded with
time.
Result and discussion:
Preliminary spectroscopic studies of
exchange of water molecules of trans[Cr(C2O4)2(H2O)2] -1 with incoming arginine(N,O ) ligand, show the intensity of absorption
band increasing at max 550nm(max) and max
trans-[Cr(C 2O 4 ) 2(H 2 O) 2 ] ArgOH 2

trans [Cr(C 2 O4 ) 2(H 2 O)OH] 2- ...... (1)

ArgO- + H + ....(2)

ArgOH + H +

Trans-[Cr(C 2O 4 ) 2(H 2 O) 2 ] -+ArgO -

Kequ =

(log Kh=7.2)

(log Ka1 = 2.17 and log Ka2 = 9.4)

cis-[Cr(C 2 O 4) 2 (ArgO)] 2- .....(3)

[cis-Cr(C 2 O 4) 2(ArgO)] 2-

........(4)
- n

(trans-Cr(C 2O 4 ) 2(H 2 O) 2 ][ArgO ]

405nm(max). This increasing in absorption

(max) with slightly change in band position of
the recanting trans complex [max=565nm
(max=32) and max=416nm (max=34.4)] was
anticipated to NO5 chromophore formation
(1,7). The log (Aobs Ao)/(A-Aobs) correspond
to log [product]/{[CrT] [product]} versus log
of total arginine concentrations shows a
straight line, as shown in fig1 with slope very
close to unity. This result sustains also 1:1
ligation complex has occur. The intercept of
Fig 1 gives conditional equilibrium constant
(log Kcon). So the values of Kequ, for reaction 3
in the form of equation 4, were calculated at
different temperatures 25, 30, 40, and 500C to
be log Kequ=4.63, 4.69, 4.76, and 4.87
respectively. These values of Kequ are
consistent with those were recoded previously
for complexion of [Cr(C2O4)2 (H2O)2]- with
bidentates glycine , alanine, histidine and
oxalate ions (2,8).
Also the rate of complexion was followed
with time, under various conditions of
temperatures and pHs 4.8 6.7 ( = 0.4 M
NaNO3). First order plots of log (Aobs Ao) vs.
time give two crossover good straight lines.
This is fit to two consecutive parallel complex
reactions with two observed rate constants
kobs1 and kobs2 of the two different starting
Cr(III) species {[Cr(C2O4)2(H2O)2]- and
[Cr(C2O4)2 (H2O) OH]2-} plus ArgOH ligand
in solution. The most striking results are the
reaction zero order depend on the arginine
concentration and one of the rates constant
(kobs1) is an acid depended while the other rate
constant (kobs2) is acid independent.
The acid dependent rate was analyzed and
found to obey the rate low kobs = k[H+]-1+k.
A typical plot of kobs1 vs [H+]-1 was shown in
Fig-2,that gives two rate constants k1 and k2
(corresponding to k and k respectively) from
slope and intercept. So overall there are three
kinetically importent reaction pathways with
rate determine steps k1, k2 and k3
(corresponded to pseudo first order kobs2) .

(n=1)

obs-A o)/( &-A obs)

0.8
0.6
0.4
0.2

log

0
-0.2
-0.4
-1.8

-1.6

-1.4

-1.2

-1

-0.8

log[Arginine]T

Fig. 1 A typical plot of log (Abos Ao)/(A-Abos) versus total log[arginine] at temperatures
30oC (), 40 oC( )and 50oC() (pH=5.6).
0.18
0.16
)

0.12

kobs (
min

-1

kobs1

y = 2.02E-07x + 0.0518
R2 = 0.9884

0.14
0.1

0.08
0.06
0.04

kobs2

0.02
0

100000 200000 300000 400000 500000 600000 700000

+ -1
[H ]

Fig.2 The effect of hydregon ion concentration on the observed rate constants kobs1 and kobs2 of the reaction of
Trans- bis(oxalato) diaquo Chromate(III) with arginine

The above result suggests that the reaction of trans- bis(oxalato) diaquo chromate with arginine
is very similar to that of our previous studies of amino acids glycine, alanine and histidine
complexation (2) and follow the same mechanism, but with the slight difference results from
hydrogen bond tendency of arginine of free NH2 and other amino groups of non leaving H2O (or
OH) on Cr(III) center. This interaction may result a relatively conjugated bases (OICB1 and
OIVB2), which are depicted below.
The pectoral illustration shows the probability that both the hydrogen bonding and the trans
effect may contribute and have strong kinetically effect on interchange rate of water substitution in
both trans-bis(oxalato)diaquo Cr(III) and its conjugated species. This was virtually observed in both
the rates and activation parameters of step k1 and k3 [see scheme below and table 2]. Therefore,
using the same assumption as in our pervious studies (2), in which k1, k2 and k3 are rate determine
steps of intermediates I1, I2 and I3 formation respectively and these intermediates are followed by
rapid rates of internal ring closer reaction to final product(P) (steady state condition) the rate laws
corresponding to the scheme below are expressed in equation 5 and 6 and the observed rate
constants in eq. 7 and 8 :
H

H
H

N
NH

O
O

CH2

Cr(III
)

H
H

CH
H

Outersphere Internal Conjugated Base via Hydrogen Bonding

(OICB2)

NH

CH2
CH2

CH2

H2O

Cr(III
)

CH2

N
NH

NH

CH2

H2O
H

CH

O
H
H
Outersphere Internal Conjugated Base via
Hydrogen Bonding(OICB1)

From the reactions 9 and10 of the scheme below the rates of product formation are:
d[p]/dt = k-4[I1]-k4[p]+k2[I2]-k-5[p] (5)
d[p]/dt=k6[I3]-k-6[p]

.(6)

k1 Kh Kos . 1

kobs1=

[H+]

Kos

+ k2 ...(7)

kobs2= k3
..(8)
According to the above equations 7,8 the
values of k1 Kos/Kos, k2 and k3 are calculated
and tabulated in table 2, at different
temperatures with activation parameters of
each rate determinant step in the reaction.
Table 3 gives some related complexation of
cis-and trans[Cr(C2O4)2(H2O)2]- .

H2O

In comparison, we can see the values of

the rate constants in arginine reactions are
higher than that for water-solvent exchange at
Cr(III) , but very similar to those values were
recorded for glycine, alanine and histidine in
our previous study (2).

ArgO
O

H2O
O

O
Cr

K'os

k1[-H2O]
,ArgOH
k -1

Cr

+ ArgOH

Cr
O

O
OH

OH

OH

Trans monaquo mono hydroxy

bis(oxalato) chromate (III) ion

Outer sphere complex

(OICB1)

trans -mono(ArgO) monohydroxy

bix(oxalato)chromate(III) ion (I1)
k-4

Kh [-H+]

O
H2O
k2[-H2O] O
O
O
Cr
Cr
,ArgOH
O
O
k -2 O
H2O
O

Kos

H2O
O

O
Cr

outer spher
complex

+ArgOH

H2O
Trans-diaquo bis(oxalato)
chromate(III) ion

H2O
k3[-H2O]
O
O
,Ar
g
OH
Cr
k -3
O
O
H2O
Outer sphere complex
(OICB2)

....(9)

O
H2O k
O
5[-H2O]
ArgO k -5

N
Cr
O

O
O

Cis-mono (ArgO) bis(oxalato)

chromate(III) ion

Cis-monoaquo mono (ArgO)

bis(oxalato) chromate(II) ion

Kos

k4 [-H2O]

H2O
O

k6[-H2O]

Cr
O

O
ArgO

Trans-monoaquo mono(ArgO)
bis(oxalato) chromate(III) ion

(I3)

k -6

.....(10)

Cr
O

O
O

Cis-mono (ArgO)
bis(oxalato) chromate(III)
ion

Scheme of the consecutive parallel reactions of [Cr(C2O4)2(H2O)2]- and [Cr(C2O4)2 (H2O)OH]2- (Kos and Kos are
outer-sphere associative constants)

Table 2 The derived rate constant values for k1 Kos/Kos,k2,and k3 and calculated activation parameters for
amino acid arginine with trans- bis(oxalato)diaquo chromate(III) ion.
Temp
. 0C
35
40
45
50
55

k1 (Kos/Kos)x102
sec1
9.76
12
12.82
15.35
8.56

Ea(Kcal/mol)= 6.14

H (Kcal/mol)= 5.51
S(Cal/mol)= -45.3

k2
x104sec-1
3.58
6.98
12
15.7
20.1

Ea(Kcal/mol)= 17.2

H ( Kcal/mol)= 16.55
S (Cal/mol)= -20.36

k3
x104sec1
1.65
1.8
2.63
2.9
3.92

Ea(Kcal/mol)= 8.85
H (Kcal/mol)=8.22
S (Cal/mol)= -49.3

Table 3 Kinetic Activation parameters for related complexation reactions

with bis(oxalato)diaquo chromate(III).

Complex
trans ' cis isomerization of [Cr(C2O4)2(H2O)]trans ' cis isomerization [Cr(C2O4)2 (H2O) (OH)]2Aquation of [Cr( C2O4)2(H2O)O2CCH3]2Aquation of [Cr (C2O4)2(O2CCH3) OH]-3
Anation of cis-[Cr(C2O4)2(H2O)2)]- with C2O4=
[Cr(C2O4)2 (H2O) +glyO Trans-,Cis- intermediates
=
+ alanO- formation respectively
=
+ HistO-1
[Cr(C2O4)2(H2O)OH + glyO=
+ glanO=
+ HistOH2Oexchange of [Cr(H2O)6]+3
[Cr(H2O)6]+3 + glyO-

H Kcal/ mol
17.5a
14.6a
16.3b
8.4 b
19.8
19.80 , 15.26c
15.15 , 12.75
15.50, 12.10
9.35 (Ea 9.97)c
8.60 (Ea 9.24)
6.67 (Ea 7.33)
26d

S e.u
-15.3
-23.0
-18.8
-34.4
-4.8
-10.9 , -22.5
-27.0 , -33.5
-18.33,-33.94
-34.47
-37.80
-46,45
+12

18e

- 23

(a)
(b)
(c)
(d)

M. Casual, G. illauminati and G.OP. Taggi, Inorg. Chemisry; II (5), 1062, (1972).
Thomas W. Kallen and Randall, E. Hamm; Inorg. Chem. 18(8), 2151 (1979).
M.Abdullah and B. Kamal submitted paper for publication (2002) .
R. Plane and H. Tube; J. Phys. Chem, 56,533 (1952). Illuminati and G. Ortaggi; Inorg. Chem. 11, 1052
(1972).
(e) M.A.Abdullah, J. Barret, and P.O Brien;J.Chem. Dalton Trans., 1647 (1984)

Therefore, this close similarly leads to the

same mechanism as we have mentioned in
previous study (2), in addition to that the
reaction took place by hydrogen bond
formation and trans-effect of OICB1 and
OICB2. These may have general great effect
on interchange water molecule with incoming
ArgO- in the both rate determinant steps and
the followed ring closure steps. The values of
k1 (Kos/Kos ) are observed larger than that of
other amino acids glycine, alanine, arginine
and monodentate SCN- substitution (2,9),
k1(Kos/Kos) = 12 x 10-2 sec1 at 400C, Ea =
6.14 Kcal/mole for arginine, while for glycine,
alamine and histidine, are 5.18x 10-2, 2.67 x
10-2 and 1.01 x 10-3 sec1 at 400C, respectively
with average Ea = 8.8 kcal/mole. But the
values of k3 are observed in the same range to
that for glycine, alanine and histidine at

different temperatures, with lower values Ea

= 8.8 Kcal/mole.This value is very similar to
that obtained in case of CrOH reaction with
the above mentioned amino acids (2) and
aquation energy of hydroxyl species,
[Cr(C2O4)2(O2CCH3)OH]3- (10). Nevertheless,
the values of k2 are also very similar to those
observed
previously
(2)
in
cisbis(oxalato)monoamino
acid
monoaquo
chromate(III) intermediate formation(I2), with
E = 17.2 Kcal/mole. Also this activation
energy is observed in the same range of trans
' cis isomerization of [Cr(C2O4)2(H2O)2]-(5),,
anation of NCS- of cis-[Cr(C2O4)2(H2O)2]-(9),,
aquation energy of Cr(C2O4)3 and [Cr(C2O4)2
(O2CCH2)(H2O)]3- (12,10), in these cases the
values of activation energies were recorded in
the range 13 18 Kcal/mole(see table-3).

The low values of activation energy (or

H ) in arginine complexation reaction of k1
and k3 may be explained on the basis of
probability hydrogen bond formation of
OICB1 and OICB2 which react faster after
hydrogen bond formation to the intermediate
I1 and I3. However, the presence of OH and
formation conjugated base as in OICB1 and
OICB2 cause great trans effect on water
exchange with low values of activations
energies.
Consequently, the data of rate constants
and activation parameters specially ve values
of (S) (table 2) for all internal exchange
water reactions in this study are consistent

with interchange associative mechanism (Ia) at

Cr(III) center and sustain to the existence of
outer- sphere conjugated base formation
OICB1 and OICB2, which are later reacting
much faster in water exchange by trans-effect
labilization (11,12). The lability of OH- has
been reported before (13,15), as to decrease
the value of activation energy or (H) by 2-6
kcal/mole. However the OH- group and that
results of outer sphere conjugated base via
hydrogen bonding are able to donate more
electron density to Cr(III) center and hence
labilize it to react more faster in water
interchange reaction.

References:
1- Thomasw. Kallen and Randall E. Hamm; Inorg. Chem (1979), 18(8),2151.
2- M. A. Abdullah and B. K.Aziz, paper submitted for publication 2002.
3- D. F. Sheriver, P. W. Atkins and C. H. Langford, Inorganic chemistry, Oxford university
(1992), ch. 15, p-477.
4- K.R. Ashely, J.8. Leipoldt and V.K.Josghi; Inorg Chem (1980), 19, 1608-1612.
5- a-M. Casula, G.Illumunati and G. Ortaggi, Inorg. Chem., 115(5), 1062(1972).
b-K. R. Ashley and I. Trent, Iorg. Chim. Acta, 163, 159(1989).
6- B.E.Dawson;Practical Inorganic Chemistry Methuen and Co.Ltd. London,2nd
ed.(1967).214.
7- Kotra V. Krishuamurty and Goron M. Harris; The chemistry of the metal oxalato
complex a chpter of chemical reviews, Vol.6(1), (1961), published by A. Chem. Soc.
8- Return to ref. 238.
9- N. V. Duffy and J. E. Ericy; J. Am. Chem. Soc. 89(1967), 272.
10- A- K. R. Ashely and S. Kulprathipanja, Inorg. Chem. 11, 444(1980).
B - Thomas W. Kallen and Randall, E. Hamm; Inorg. Chem. 18(8), 2151 (1979).
11- J. Benjamin Coe and S.J. Glen Wright; Trans-effects in octahedral transition metal
complex, coordination chemistry reviews, Vol. 203 (1), 5 80 (2000).
12- Ryuni Nakata, Kimio Isa and Hisaya Oki; Analytical Science, 17,453-456 (2001).
13- H. Taube Chem. Rev. 50, 69 (1952).