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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-
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
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
ArgOH + H +
Kequ =
(log Kh=7.2)
[cis-Cr(C 2 O 4) 2(ArgO)] 2-
........(4)
- n
(n=1)
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
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
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
ArgO
O
H2O
O
O
Cr
K'os
k1[-H2O]
,ArgOH
k -1
Cr
+ ArgOH
Cr
O
O
OH
OH
OH
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
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
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)
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