-
-
10- -
(28-29 2014 )
2014
-
2
(V)
* .., .. *
- . . , - . , [R-S-S-R]/[RS]2, RS-3--1,2,4--5 2/, 4 /, 6 / HCl
298, 250,14; 226,98 211,5. , 0, . , 273 338 0 6/ HCl 183,5 273,2. ,
HCl - E0. , 6/ HCl 273-338 E0 89,7, 4/ 2 / HCl 84,3 75,5 . , HCl
E0. E0 1,2,4-. E0 :
2-ThioPir < 2-M < I-Met-2M < Pthiol <
3-Met-1,2,4-Tthiol <
129,9 165,3 179,0 184,8 209,5
< 3-t-1,2,4-Tthiol < 1,2,4-Tthiol < 3,4-DiMet 1,2,4-
Tthiol <
211.5 266,0 290,3
-
3
< 4- Met-1,2,4-Tthiol
-
4
(-) - , , 3, , . . , , , , , , , . . - [3].
1. .., .., .. . .
: , 2007. 298 . 2. .. //
. IV . . -2010, 28-29 2010 ., , 2010. - 54 . . 37.
3. 2523892. . .., .., .., .. . 27.07.2014. . 21.
CHCl3
.., * .., ..
, . , , * , . ,
() () (I-, NO3
-. SCN
-, CCl3COO
-, ClO4
-) .
- , - [Sc()3]I3, [Sc()3](NO3)3, [Sc()2(SCN)2]SCN,
-
5
[Sc()2(CCl3COO)2]CCl3COO [Sc()3](ClO4)3. CHCl3 . [Sc()3](ClO4)3,
CHCl3.
. , , (k:103-,-1) :
SCN- (5,99) > I
- (3,56) > NO3
- (2,25).
, (): I
- -
3,4510-13; NO3- - 1,0310-13; SCN- - 5,0410-13; ClO4
- - 2,210-15; CCl3COO
- -
4,1110-14. .
, , - . , 6 / HCl + 1 / NaClO4 Sc(III) 0,05 / CHCl3 , , Cu(II),
Co(II), Ni(II), Zn(II), Cd(II), Mn(II), Al(III), Cr(III), Zr(IV),
Th(IV), V(V).
(V) 1--2- 7/ HCl 273
* .., .., .., ..
* ,
*
(V) , . (+5) . (V) . , .
-
6
. (V) , 1--2- 7/ HCl 298. (V) 1--2- 7/ HCl 273 (.1).
.1. (V) c 1--2-
7/ HCl 273
, 2[ReOCl5]- 1--2--7/ HCl 273 pKi: pK1=5,98; (2=9,5510
5) 2=4,86; (2=7,2410
4) 3=3,96; (3=9,12103) 4=3,29; (4=1,9510
3) 5-=2,89; (5=7,7610
2 ). ( 1).
, .
- ; [L]- 1--2-. Excel Borland Delphi, Windows 7. 5=0 . 1--2- 0,1
5,0 0,1. (V) 1--2- 7/ HCl 273 ( 2).
-
7
.2. (V) c 1--2-
7/ HCl 273,
. 2 pKi
:n*
1 =6,06 (1*=1,15106);
*
2 =4,90 (2*=7,941,15104);
*
3 =4,02; (3=1,05104);
*
4 =3,35; (4*=2,24103);
*
5 =2,65; (5*=4,47102).
, pKi -1--2- (V) . pK5.
*
i
2[ReOCl5]- 1--2--7/ HCl 273 (.3).
. 3. (V) 1--2-
7 / HCl 273
i) 1--2- (V) 273 7/ HCl .
-
8
1--2-
(V) 7/ HCl 273
maxi
[ReOLCl4]-
5,6
[ReOL2Cl3] 4,6
[ReOL3Cl2]+ 3,8
[ReOL4Cl3]2+
3,2
[ReOL5]3+
2,6
,
max
i 1--2-.
(V)
* ..., ..
* ,
. , , . (V) . (V) . , , (V). (V) 2 1--2-.
[ReO(2-M)4]222 900 (
) 120 0 ( ) -, . . 380 0 - . . [ReO(2M)23]22
-
9
90-100 0. , 260 0. : [ReO(2M)4r2]r222 400
0 43,7, 70,0. , 2- , . 1--2- (V).
[ReO(2-M)2r3] 22 c (V) 1-Met-2-M , 2- . , -2- 2600, 1--2- 3600.
, 2- 1--2- , . , -, 1--2- .
(III) , ,
( ) ,
.., * .., .., .., ..
, . , , * ,
. ,
(III) . , 350 , (), () (, Br, ), HCl, . 1,8-2,2 . HCl, . , Fe
(III). HCl
-
10
0,25 4,0 / (99 %) 3 4 / HCl. Br 2,0-4,0 / HCl.
() Fe (III) , . HCl H2SO4, (H2SO4) 0,25 /. , , HCl, 1 / (, ),
0,5 / (Br) NaCl KCl 1 / Fe (III) 92 94 %. [FeCl4]
1- ( . H)Cl.
(III) Br , : 99,32 Fe (III) 19,2 0,1 ; Br 98,76 Fe (III) 19,2
0,1 / 17,8 17,7 0,1 / FeCl3 .
R : H+ : Fe3+ : Cl- : = 2 : 2 : 2 : 7 : 0,9, (RH)[Fe2Cl7]
. RH(Br), R .
(Br) HCl H2O (III), .
-
.., .., .., ..*
, . , , * , . ,
() () Ca(II), Mg(II), Sr(II), Ba(II), Co(II), Ni(II) Cu(II) .
Ca(II) Cu(II) CHCl3
-
11
(0.05 /) NH3
0,1-0,8 / (.). Sr(II), Ba(II) Co(II) NH3 (NH3)=0,25-0,80 /.
Ni(II) (NH3)=0,1 /. 9:1. pH50 Ca (7,3) < Sr (8,1) < Ba (8,5),
lgD Ca Ba. 10% pH50 Ca(II) 6,0, Mg(II) 6,2. pH50 : Co (4,3) < Ni
(4,10) < Cu (1,3).
CHCl3 , Mg(II) Ca(II) NH3 0,1-0,5 /.
Ca Mg 0,1 / CHCl3. D(Ca) 5,2, D(Mg) 2,6. . , , (NH4)2CO3 Cu(II)
Ni(II), Co(II) 93% ((NH4)2CO3)>0,5 /. (II).
lgD(Me)-lgC(R) R:Me=2:1. Cu, Co CHCl3: 2HR() +
[Me(NH3)4](NO3)2() [MeR2](o) + 2NH4NO3() + 2NH3(), Me Cu,
Co, Ca
2HR() + [Ni(NH3)4](NO3)2() [Ni(NH3)2R2](o) + 2NH4NO3()
[Me(H2O)R2](o).
(II) CHCl3 , , .
-
12
Potentiometric and thermodynamic investigation of rhenium(V)
complexes
with 4,5-dihydro-1H-imidazole-2-thiol
Gouda G.A., *Aminjanov A.A.
Faculty of Science, Al-Azhar University, Assiut, 71524,
Egypt
*Tajik National University
Corresponding author. E-mail: [email protected]
Stability constants of 4,5-dihydro-1H-imidazole-2-thiol with
rhenium(V)
were determined potentiometrically in acidic medium (4 M HCl) at
different
temperatures. The dissociation constants pK of
4,5-dihydro-1H-imidazole-2-thiol
as well as the stability constants (lg K) of their complexes
were determined at
varieties temperatures. The corresponding thermodynamic
parameters (Go, Ho and So) were determined and discussed. The
formation of the metal complexes has been found to be
exothermic.
Key words: Potentiometric, rhenium(V), formation constants,
thermodynamics.
Characteristic stability constants may be important for
predicting various
chemical processes, such as isolation, extraction and
concentration methods,[1,2]
since many elements are present in trace amounts, and can be
separated by
complexion reagents. Bejerrums[3] dissertation being initiative
in developing this field. Metal complexation not only brings the
reacting molecules together to give
activated complex [4]
but also polarized electrons from the ligands towards the
metal. The relation between stability and basicity of the
ligands is indicated by the
formation constant and free energy change values. The stability
constant dependent
on several factors such as: electronegativity, hardness or
softness of the donor
atoms on the ligand, the metal ion, nature of the ligand, the
ionic radius and charge
of the oxidation state on the metal core respectively. One
available method is the
potentiometric titration using ligand redox electrodes based on
sulfur compounds
and their oxidized forms. Many workers [5-18]
have reported their results on metal-
ligand stability constants and their oxidized forms.
Experimental
To determine the formation constants of rhenium(V)-
4,5-dihydro-1H-
imidazole-2-thiol in 4 M HCl at different temperatures a
potentiometric method of
employed. Equilibrium concentrations of
4,5-dihydro-1H-imidazole-2-thiol are
calculated by the following equation:
all
initialinitial
Liinitial
V
VC
T
EEL lg
2
1lg
109837.1]lg[
4
where Einitial - initial equilibrium potential of the
oxidation-reduction system
in the absence of rhenium(V); Ei - equilibrium potential at end
point of titration. initial
LC - initial analytical concentration of
4,5-dihydro-1H-imidazole-2-thiol;
Vinitial/Vall - the ratio of the initial volume to the total
volume of the system: T - the
-
13
temperature of the experiment in Kelvin degree. Determined at
each point of the
titration equilibrium concentration of the ligand. The function
n was calculated at each titration by the formula:
)Re(
][
V
L
C
LCn
where n is the average degree of formation derived from the
titration curves of a ligand with metals; CL is the concentration
of 4,5-dihydro-1H-imidazole-2-
thiol; [L]- equilibrium concentration of
4,5-dihydro-1H-imidazole-2-thiol; CRe(V)-
the concentration of rhenium(V). All the calculations are
employed using a
computer Intel Core i7. Results and discussion
Among the ligand redox electrodes used for the study of
complexes represent an
important type on the basis of sulfur-containing organic
compounds and their
oxidized forms. The preparation of such electrodes is based on
the reversible
oxidation of thione or thiol-containing compounds to the
corresponding disulfides.
The synthetic method[19]
involved the synthesis of 4,5-dihydro-1H-imidazol-2-thiol
by refluxing 1,2-diaminoethane and carbon disulphide. The
synthesis route of
compounds is outlined in the following:
The complexation process of rhenium(V) with
4,5-dihydro-1H-imidazole-2-thiol
proceeds stepwise and reversible. It is natural that the
stability of these complexes
depends on the nature of the substituent in the
4,5-dihydro-1H-imidazole-2-thiol.
The addition of H2[ReOCl5] to a solution (0.0759 M) containing
4,5-dihydro-
1H-imidazole-2-thiol (0.0259 M) and its oxidized form in the
acid medium (4 M
HCl) causes a change in color of solution to deep green, with
increasing
concentration of H2[ReOCl5] the solution is changed to purple,
blue and finally to
green. The adding, to the green solution
4,5-dihydro-1H-imidazole-2-thiol color
change of the solution is reversed. This fact indicates the
gradation and
reversibility of the complexation of rhenium(V) with
4,5-dihydro-1H-imidazole-2-
thiol. In the titration of rhenium(V)-
4,5-dihydro-1H-imidazole-2-thiol system and
its oxidized form, an increase in the magnitude of the
equilibrium potential,
indicating a other participation in complexation of rhenium(V)
with 4,5-dihydro-
1H-imidazole-2-thiol than its oxidized form. At each point,
equilibrium is
established within 5-10 minutes. By potentiometric titration
each values of the
equilibrium concentration of 4,5-dihydro-1H-imidazole-2-thiol
and E are
determined. Using values of [L] and taking together with both
the analytical
concentrations of H2[ReOCl5] and
4,5-dihydro-1H-imidazole-2-thiol formation
constants can be calculated. Some data determined by
potentiometric titration of
-
14
rhenium(V) with 4,5-dihydro-1H-imidazole-2-thiol in 4 M HCl at
273 oK, are
presented in Table 1.
Table 1. Data obtained by potentiometric titration of rhenium(V)
with 4,5-dihydro-
1H-imidazole-2-thiol in 4 M HCl at 273 oK
Re(V).103 L.10
2 , mV -lg [L] n
Mole/l
4.536 2.323 61.54 2.745 4.73
4.773 2.309 74.54 2.986 4.62
5.240 2.281 108.98 3.624 4.31
5.808 2.247 155.54 4.487 3.86
6.358 2.214 178.98 4.923 3.48
6.892 2.182 185.21 5.041 3.17
7.413 2.151 188.32 5.101 2.90
7.917 2.121 193.21 5.195 2.68
8.409 2.092 196.47 5.258 2.49
8.886 2.063 199.14 5.310 2.32
9.351 2.035 201.44 5.355 2.18
10.245 1.982 203.35 5.396 1.93
11.092 1.931 207.24 5.474 1.74
12.664 1.837 215.57 5.638 1.45
14.089 1.752 220.54 5.740 1.24
14.754 1.712 225.32 5.834 1.16
15.996 1.638 228.62 5.904 1.02
17.135 1.570 230.87 5.955 0.92
18.184 1.508 233.36 6.010 0.83
19.608 1.422 236.56 6.081 0.73
20.881 1.346 238.47 6.128 0.64
22.024 1.278 240.21 6.172 0.58
23.692 1.178 244.55 6.270 0.50
25.118 1.093 246.08 6.314 0.44
Figure (1) showed potentiometric titration formation curves of
rhenium(V)-
4,5-dihydro-1H-imidazole-2-thiol complexes at different
temperature in 4 M HCl.
-
15
Fig. 1. Plots of n against (-lg K) for rhenium(V) with
4,5-dihydro-1H-imidazole-2-thiol complexes in 4 M HCl at different
temperatures.
Potentiometric titration curves showed that
rhenium(V)-4,5-dihydro-1H-
imidazole-2-thiol system in presence of 4 M HCl at different
temperatures
consistently produced four types of complexes. The log Ki values
of rhenium(V)
with 4,5-dihydro-1H-imidazole-2-thiol from the titration curves
by Bjerrum
method at half-integer values [20-21]
of the degree of formation ( n ) is presented in Table 2.
Table 2. Formation constant values of
rhenium(V)-4,5-dihydro-1H-imidazole-2-
thiol in 4 M HCl at different temperatures
T, oK
[ReOLCl4] [ReOL2Cl3] [ReOL3Cl2]
+ [ReOL4Cl]
2+
lg K1 lg K2 lg K3 lg K4
273 6.27 5.61 5.26 4.92
288 6.10 5.43 5.10 4.71
298 5.81 5.17 4.86 4.53
308 5.55 5.03 4.64 4.31
318 5.31 4.78 4.48 4.10
328 5.13 4.65 4.39 3.45
338 5.02 4.57 4.32 3.11
These data show that with increasing amount coordinated
molecules 4,5-
dihydro-1H-imidazole-2-thiol lg Ki decreases. Stepwise formation
constant ratios
were as follows: K1/K2 = 4.57; K2/K3 = 2.24; K3/K4 = 2.19 at 273
oK. These data
indicate that the ratio stepwise formation constants are not so
large enough, so it
was necessary to clarify the estimated constants either
successive approximation
method or by the "pH-meter program [22]. However, attempts to
refine the estimated formation constants were not sufficient.
The equilibrium constant (K) varies with temperature according
to the Van't
Hoff [23-24]
equation:
R is the universal gas constant, T is the absolute temperature
(in oK) and Ho is the
enthalpy change. To obtain the integrated equation, it is
convenient to first rewrite
the Van't Hoff equation as
Thus, for exothermic reactions, the Ho is negative and K
decreases with temperature, but for endothermic reactions Ho is
positive and K increases with temperature. In accordance with the
data
[25] values of stability constants after
verifying these methods vary slightly. In this regard, the
stability constant of
rhenium(V)-4,5-dihydro-1H-imidazole-2-thiol complexes, some of
the
potentiometric titration curves, were used to estimate the
thermodynamic
-
16
properties of the complexation by the temperature coefficient.
The Ho values were determined from the slope of the straight line
obtained by plotting log Ki
against 1/T (Fig. 2). The change in entropy is determined by the
interval intercepts on the y-axis, these lines (So = R *
interception)
[26,27]. Gibbs energy
[28] was
calculated from the equation Go = Ho-TSo (Table 3).
Calculated
thermodynamic function showed that the isobaric-isothermal
capacity becomes
less negative with increasing number of coordinated molecules of
4,5-dihydro-1H-
imidazole-2-thiol. This experimental finding may be due to an
increase in the steric
hindrance that prevent in entering molecules of
4,5-dihydro-1H-imidazole-2-thiol
to center the inner sphere complexes [29]
.
2.5
3
3.5
4
4.5
5
5.5
6
6.5
7
2.9 3.1 3.3 3.5 3.7 3.9
log i
1/*10-3 (oK-1)
1
2
3
4
Fig. 2. Plots of log Ki against 1/T for rhenium(V)-
4,5-dihydro-1H-imidazole-2-
thiol complexes in 4 M HCl at different temperatures.
Table 3. The thermodynamic parameters of the formation
rhenium(V)- 4,5-
dihydro-1H-imidazole-2-thiol complexes in 4 M HCl at different
temperatures
Species -Ho, kJ/mole -Go, kJ/mole -So, J/mole
[ReOLCl4]
36.97 32.88 13.70
[ReOL2Cl3] 22.36 28.97 3.05
[ReOL3Cl2]+ 27.84 27.65 0.65
[ReOL4Cl]2+
48.78 24.99 79.86
The values of the entropy changes for the mono-substituted
complex compared
to the disubstituted complex have a much greater significance
[30]
. Thus, as the
higher value of So can be interpreted in favor substitution of
chloride ion in the trans-position to the oxygen oxorhenium groups
is apparently due to the fact that
Re-Cl distance being in trans-position to the oxygen of the
oxorhenium group in
the equatorial plane [31]
. Significant decrease of So is probably due to the fact
that
-
17
the introduction of a second molecule of
4,5-dihydro-1H-imidazole-2-thiol in the
inner coordination sphere becomes more difficult and that such
molecule may
replace one of the four chloride ions that are in the equatorial
plane [32]
.
Mole fractions are commonly used to calculate the concentrations
of the
individual complexes on the basis of the formation constants.
Mole fractions of a
particular form of the complex compressed as ratio of the
concentration of the
complex to the total concentration of the metal ion
([MLi]/[Metal ion] = Xi). To
determine the field dominance of a complex in the form of
rhenium(V)-4,5-
dihydro-1H-imidazole-2-thiol in 4 M HCl was calculated from the
distribution
curves at different temperatures. Figure 3 shows the
distribution curves of complex
models at 328 oK.
0
0.2
0.4
0.6
0.8
1
0
0.2
0.4
0.6
0.8
1
1 2 3 4 5 6 7
Xi
-lg[L]
X0
X1
X3
X2
X4
Fig. 3. Distribution curves of rhenium(V)-
4,5-dihydro-1H-imidazole-2-thiol
complexes at 328 oK; where X0 = [ReOCl5]
2-, X1 = [ReOLCl4]
-, X2 = [ReOL2Cl3],
X3 = [ReOL3Cl2]+, X4 = [ReOL4Cl2]
2+.
Analysis of the distribution curves show that increasing
temperature has
little effect on the proportions of the maximum output value for
all complexes.
Increasing temperature causes Ximax
being shifted towards higher values of
equilibrium concentration of 4,5-dihydro-1H-imidazole-2-thiol
(Table 4).
-
18
Table 4. The Ximax
output equilibrium values for rhenium(V)-4,5-dihydro-1H-
imidazole-2-thiol complexes in 4 M HCl at different
temperatures
Species Values -lg [L] at Xi
max
273 oK 288
oK 298
oK 308
oK 318
oK 328
oK 338
oK
[ReOLCl4]
6.0 5.8 5.6 5.4 5.2 5.0 4.8
[ReOL2Cl3] 5.4 5.2 5.0 4.8 4.6 4.4 4.4
[ReOL3Cl2]+ 5.0 4.8 4.6 4.4 4.2 3.8 3.6
Based on these data it is possible to choose the optimum
conditions for the isolation of
certain complex, establishing their composition and
structure.
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-
19
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(CnH2n+1)4NReO4 (1
-
20
Tc (C5H11)4NTcO4 ( NaNO3) (1 1,2) HNO3 , (1,5 8,5) 10
-2 /
4 HNO3, 7,510-8
/ 239PuO2(NO3)2 4,3 / 106
Ru(NO)(NO3)3, 239Pu 106Ru (1,2
2,5)102 (6,8 8,5)102 . (C6H13)4NMeO4 ( ), - Tc.
( ) (C3H7)4NTcO4 (C5H11)4NTcO4 , a = 3,98 TcC1-x 0,61 < x
< 0,85 . , 94 % 6 % , (C3H7)4NTcO4, (C5H11)4NTcO4 (C5H11)4NReO4
.
, . , , (. NbCl6) CH2 , (=20 3).
(CnH2n+1)4NMO4 (=Tc, Re ; n=3, 5, 6) .
- - - - . 20 /.
- , , , .
(1-2 . %) , .
-
21
(V) 1--2- 4,5 / HCL 298
.., .., ..
- 1--2- H2[ReOCl5]1--2- 4,5/ Hl 298. , , : 1=2,310
5; 2=1,3104; 3=1,010
4; 4=4,1102.
(V) 1--2- . i 1--2- (V) 4,5 / 5,5 / HCl 298 , . , 298 1 4,5 /
HCl 2,3105, 5,5 / HCl 8,1105. 2 HCl 4,5 5,5 / 1,3104 7,0104.
H2[ReOCl5]1--2- 4,5 / HCl 298 .
. -1--2- (V) 4,5/ HCl 298 , 0-[ReOl5]
2, 1-[ReOLl4]
, 2-[ReOL2l3], 3-[ReOL3l2]+, 4-[ReOL4l]
2+
-
22
. *., . *., . .** , *,
**,
, , , , . . . - . , . , . , , . -. , , , -, , , . . -, : . , 10
% . . . [Zn(NH3)4]SO4, - [Zn(NH3)4](ReO4)2. :
ZnSO4 + 4NH4OH = [Zn(NH3)4]SO4 + 4H2O,
-
23
[Zn(NH3)4]SO4 + 2NH4ReO4 = [Zn(NH3)4](ReO4)2 + (NH4)2SO4.
:
[Zn(NH3)4](ReO4)2 + 4H2O = Zn(OH)2 + 2NH4ReO4 + 2NH4OH,
[Zn(NH3)4](ReO4)2 + 2H2SO4 = ZnSO4 + 2NH4ReO4 + (NH4)2SO4.
. , %: 86 , 99 , 96 . .
,
.., .., .., .. , ,
, .
- . - . Re. , - .
Re- ( ) , . - Re- , Re ( 924 -1, ReO4
-).
- (20-100 /3) ReO4
-, .
-
24
Re . Re- (3-20 / NaF)
3(F4) ReO4- 924 -1
(900, 915, 930 -1), .
Re . Re , .
Re, , . Re 4, .. 1:4. , ReO4
-
4. , 1:1 1:4, ()
(G) : 1:1, 1:2, 1:3. :
:
Re Re
G, / G, /
1:1 3,8010-3 13,79 7,2010-3 12,22
1:2 6,2210-7 35,39 1,3310-4 22,11
1:3 2,0010-8 43,90 6,2210-7 35,38
Re , , Re .
[ReO(H2Cit)4(OH)2]
-, - [ReO2F4]
-.
-
25
.., .., .., .. , . , . , 101, -mail:
[email protected]
, , , . , Re2O7 3. .1 50 60% Re 90% . .2
, , .
- , , , , . , , . - (. , ).
: 1.
, SO2 - .3
2. .
3. Purolite -172, .4,5
-
26
1. .., .., .., ..
// - . 2011. 12. . 170-175.
2. .., .., .., .. // . 2011. 4. . 221-229
3. .., .., .., .. 2393253, . 18, 27.06.2010
4. .., .., .., .., .. , // XI - . : - , 2012. . 4-8
5. .., .., .., .., .. , // IX - . .: , 2012. . 455-457
(V)
(V)
1 .., 1 .., 2 ..
1 .., 1 .. 1 ,
2
, .. . . (Pb4Re3Mo3)S16 , , . .
-
27
, , , . . VI VII . Mo (IV) Re (IV) 0,68 0 0,67 0. . . , + 4 -
S2, ReS2 . , .
- -, -, - - . (V) Re (V) (S),1--2-
(1-Met-2-Mi),1,2,4-(1,2,4-Triaz), 1,3,4-(Thiad) .
, - (V) Re (V) , . , Mo(V) Re (V) . , (HCl, H2SO4, HNO3) (HCOOH,
CH3COOH) (V) Re(V) :[OL(SCN)2(2)] , [ReOL(SCN)2(2)] [OL23]2H2O,
[ReOL23]22, [OL4]22, [ReOL4]32 ,L-SC, 1-Met-2-Mi, 1,2,4-Triaz
1,3,4-Thiad.
, =____=, (-, Re) . . [Mo2O3L2(H2O)2Cl4]2H2O,
[R2O3L2(OH)2Cl2]2H2O,
*[Mo2O3L4Cl4]2H2O
[R2O3L2(OH)2Cl2]2H2O*,
[Mo2O3L4Br4]2H2O, [Re2O3L4(NH3)4]4 22 , ,
-
28
. - .
, (V) Re(V) .
, (V) Re(V) - - , , (V) (V), .
, , , . , (V) Re (V) . (V) - 1-Met-2-Mi,1.2.4- -Triaz,
1.3.4-Thiad :(N2H5)2[Mo2O4L(OH)4(H2O)],(N2H5)2[Mo2O4L2(OH)4],
(N2H5)2[Mo2O4L2(24)2],
(N2H5)2[Mo2O4L2(SN)2(OH)2],(N2H5)2[Mo2O4L2l4] , 24., (V) - . , (V).
SC, 1- Met-2-Mi, (V) Re (V) , (). (V) (V). - (V) (V) , .
(II) 3--1,2,4--5
6 / l 273
.., ..
[1.2] (II) 1,2,4--5 1-6 / HCl 273-338 .
-
29
[3] (II) 1,2,4--5 (NaNO3) . , - (II) 3--1,2,4--5.
(II) 3--1,2,4--5 6 / HCl 273 . - 3--1,2,4--5 273 (II) 6 / HCl. ,
CuCI2 3--1,2,4--5 6 / HCl . (II) 3--1,2,4--5 (.).
(II)
3--1,2,4--5 6 / HCl(273).
T, 1 2 3 4
273 4,98 3,82 3,30 2,93
(II) (.), 3--1,2,4--5 6 / HCl 273, .
. (II) 3--1,2,4--5 6 / HCl 273 ,0-CuCl2;
1-[CuL(H2O)2Cl]+; 2-[CuL2(H2O)2]
2+; 3-[CuL3(H2O)]
2+; 4-[CuL4]
2+.
-
30
, 4- 3--1,2,4- (II) 6 / HCI.
1. .., , ..
(II) 1,2,4--5 6 / HCI 298 // . 2011. -.54, 9. .759-764
2. .., , .. (II) 1,2,4--5 6 / HCI 288 // , 2011.-.71. 7.
.19-22.
3. .., .. (II) 1,2,4--5 0.01 / // . 2012 .55, 6 -. 471-477.
--
.., .., .. - ,
360032, . 446, .33. [email protected]
- .
. . , Vll 6- d-. Re . Re (Vll) Re (lV, V) SnCl. Re n10-4 %
Re.
, . , Re .
-
31
. .
Re (Vll) - (-) , - =520, Re (Vll) - =560. =7,6 2 , Re: -=2:3, Re
(Vll) n10-10 / . Re, .. . n10-18- n10-21 / .
(V) (II) C 1--2,3--5- 6 /
I 318
.,. .., .., .. ,
. , , . (V) (II) 1--2,3--5- 6 / I 318 . , (V) 1--2,3--5- 5-- , :
1=3,2310
4; 2=9,33103; 3=4,6710
3; 4=2,18103;
5=1,51102 ( ).
[1] : *
1 =5,24104; *
2 =1,15104; *
3 =4,36103; *
4 =1,38103 *
5 =1,26102
. (II) 1--2,3--5- 4- : 1=5,63 (1=4,2610
5); 2=4,45 (2=2,8110
4); 3=2,57 (3=3,71102); 4=2,45 (4=2,8110
2). *
ip (* ):
*
1p =5,70 (*
1 =5,01105); *
2p =4,40 (*
2 =2.51104); *
3p =2,87 (*
3 =7,41102);
*
4p =2.12 (*
4 =1,31102).
-1--2,3--5- (II) 1--2,3---5- (V) ,
-
32
. , *
1 *
1
9,56 , *2 2,18 .
*
3 *
4 *
3 *
4
5,88 10,53 . 4 1,221015, 3,011015. 2.47 (II) 1--2,3--5-.
1. .., .. . . . , 1983, .28, 12, . 3090-3094
(N --)
.. ,
. , , , . , , N-- , , , .
N-- , , . . .
-
33
. , , - . 4 : 1) - ( )
. - , - , - .
2) ij : Sji = jid = 0 (ij )
3) , : 1 = 2 = 3 = .= i = j id =
4) ji ji =j id .
, , . . , . N--- () , .
(+4)
..,1 .., 1 .., 2 ..2 1 "-
", , , [email protected]
2 .., ,
- , . [1] (3+), -- , ( EtAlCl2 ) [2]. , ,
-
34
. , - - () -(). , , .
, 1,1- . , , - 1- .
ca b
a) COCl2, Et3N, Et2O b) R-2-OH-C6H3-CHO; CoCl2*6H2O; c) Et3N,
TiCl4
Ti:Al:Mg 1:500:200.
1. S. Padmanabhan, S. Katao, K. Nomura, Organometallics, 2007,
26, 1616.
2. Abbo H. S., Mapolie S. F., Darkwa J., Titinchi S. J. J. J.,
Organomet. Chem.,
2007, 692, 5327.
14-43-01014
-
35
L+2.18%FE, 0,03%
NACL
.., .., .., .., ..
.. ., . ,
, . , , . l+2.18%Fe. 0.005 0.5 .%. - (2.18%) (5%). , . 8 140 . (
50% 50% ). . , , , 0,03%- NaCl ( 4233-77). -200 ML-8. . -50-1 2 /,
NaCl. , . , 0,005-0,5% . NaCl , , ( 1).
-
36
1 - Al+2.18%Fe, , 0,03% - NaCl NaCl.
, .%
- .. -. -.. -.
/2 /2.
-
0,005
0,01
0,05
0,1
0,5
0.680
0.620
0.600
0.530
0.500
0,484
0.965
0.950
0.925
0.900
0.880
0,860
0.500
0.480
0.460
0.450
0.420
0,400
0.650
0.640
0.620
0.600
0.600
0,584
0.92
0.74
0.68
0.60
0.52
0,50
3,1
2,48
2,28
2,01
1,74
1,67
, 0.005-0.5% , Al+2,18%Fe.
4- 1,2,4- (II) 6 / HCl
.., .., ..
(II) 4--1,2,4--5 6 / HCl 273-338. . i 4--1,2,4- Cu (II) 6 / HCl
273 : : 1=3.93(1=8.5110
3); 2=3.46(2=2.88103);
3=3.23(3=1.70103); 4=3.08 (4=1.2010
3); : *i (
*
i ):*
1 =4.19(*
1 =1.55104);
*
2 =3.58(*
2 =3.80103); *3 =3.22(
*
3 =1.66103); *4 =2.73(
*
4 =5.37102);
*i (*
i ) 4--1,2,4-
(II) 6 / HCl 273, *i (*
i ):
(V) 4--1,2,4- -5, 6 / HCl 273 , i , : 1 = 3.69; 2 =2.85; 3 =
2.11; 4=1.41 1=4,9010
3;
2=7,08102; 3=1,2910
2; 4=2,6101).
( .).
-
37
1 4-
-1,2,4 (II) 6 / HCl
-,/ -G,/ S,/
[CuL(H2O)5]Cl2 14,06 22,62 28,71
[CuL2(H2O)4]Cl2 12,30 19,49 24,11
[CuL3(H2O)3]Cl2
11,05 17,60 21,98
[CuL4(H2O)]2Cl2
9,70 14,94 17,58
, . 1 , 4--1,2,4- -5 G . .
Al+2.18%Fe,
3%- NACl
.., .., .., .., . . ..
, , . , , . l+2,18%Fe. 0,005 0,5 .%. - , . 8 140. ( 50% 50% ). .
, , , 3%- NaCl ( 4233-77). 200 ML-8. .
-
38
-50-1 2 /, 3%- NaCl. , - . , 0,005-0,5% . , , .(.1).
1 - Al+2,18%Fe,
3%- NaCl
- , .
%
-.. -. -.. -. i10 10
/2 /2
- 0.860 0.994 0.600 0.620 0.170 5.70
0.005 0.860 0.998 0.550 0.580 0.162 5.42
0.01 0.848 0.970 0.534 0.580 0.150 5.03
0.05 0.832 0.960 0.518 0.562 0.146 4.89
0.1 0.818 0.954 0.500 0.540 0.134 4.48
0.5 0.800 0.925 0.480 0.522 0.130 4.35
, 0.005-0.5% 50% , Al+2,18%Fe.
(III) (V) C 1--2,3--5- 6 /
I 308 .., .., ..,
.. -
(V) 1--2,3--5- 6 / I 308 . (III) 1--2,3--5- (V) (III). (III)
1--2,3--5- 5 , : 1=5.41(1=2.5710
5);
2=3.61(2=4.07103); 3=3.32(3=2.0910
3); 4=3.05(4=1.12103);
5=2.79(5=6.16102).
-
39
*
i (*
i ):*
1 =5.42(*
1 =2.63105); *2 =3.88(
*
2 =7.58103);
*
3 =3.36(*
3 =2.29103); *4 =3.00(
*
4 =1.10103); *5 =2.47(
*
5 =2.95102).
(V) 1--2,3--5- , pKi (Ki)
n : 1=4.85(1=7.0710
4); 2=4.23(2=1.70104); 3=3.87(3=7.4110
3); 4= 3.47(4=2.9510
3); 5=2.30(5=1.99102).
*i (*
i ):*
1 =5.03(*
1 =1.07105);
*
2 =4.31(*
2 =2.04104); *3 =3.79(
*
3 =6.16103); *4 =3.12(
*
4 =1.31103);
*
5 =1.86(*
5 =7.2101).
*i -1--2,3--5-
(III) 1--2,3--5- (V) , *
1 *
5 -1--
2,3--5- (III) 2.46 4.1 , . , 1--2,3--5- (V) (III) 2.69, 2.68,
1.31 . (III) ( *5 = 1.3410
18)
1.05 ( *5 = 1.2810
18).
VO3+ - VO2+/VO3+
.., ..
- . - v2+/vo3+ vo
3+ 2,4 /,
.
v4+/v5+ . v2+/vo2+
0,8 1,03. v2+/vo3+ .
-
40
- v2+ vo3+ VOSO4 NH4VO(SO4)2. v2+ vo3+ , - . v2+/vo3+ v2+ . . 1
lg[v3+]/[vo2+] 298.
.1. lg[v3+]/[vo2+]
, = f(lg[v3+]/[vo2+]) 0,058, . v2+/vo3+, lg[v3+]/[vo2+] 298,
0,596.
, v2+/vo3+, 298 2,4 / 397 195B. E=f(lgCThio) , vo3+, . vo3+ , .
, Fi [Thio] . Fi [Thio] , 1=1,6*10
5, 2=4*107
.
(V) [ReOL4Br]Br22H2O
-
41
.., .., .. ..
-
, . , , , , /1/. , , . , , , /2/.
/3-4/.
(V) , , .
. (V) . 0,000001 0,01%. . . 18-24 , 251 /5/. .
1
(V) c .
1
-
42
(V)
, %
-
1 2 3 4 (2)
45 39 42 43 42,2 -
85 79 89 74 81,7 -
, 0,0001%
48 67 71 66 63,0 20,8
90 88 95 90 90,7 9,0
(V), 0,0001%
60 63 59 67 62,2 20,0
95 96 96 94 95,2 13,5
(V), 0,00001%
49 50 61 74 58,5 16,3
96 93 97 96 95,5 13,8
(V), 0,000001%
51 49 54 67 55,2 13,0
95 93 98 94 95,0 13,3
(V), 0,0000001%
49 51 46 42 47,0 4,8
80 74 64 72 72,5 -9,2
[ReOL4Br]Br22H2O . 2, , (V) 0,001-0,0001%. 0,0001-0,00001%.
-
43
2 (V)
,
,
,
(2) 16,6 13,5 - - ,
0,01% 17,8 16,3 1,2 2,8
(V), 0,001%
18,4 9,7 1,8 -3,8
(V), 0,0001%
18,5 15,2 1,9 1,7
(V), 0,00001%
17,5 18,5 0,9 5,0
(V), 0,000001%
16,8
13,6 0,2 0,1
(V) (. 3).
3 (V)
,
,
,
,
1 2 3 1 2 3 (2) 0,43 0,68 0,40 0,50 4,32 5,38 4,28 4,66
, 0,005% 0,71 0,66 0,56 0,64 4,10 4,91 5,42 4,81
(V), 0,001%
0,45 0,53 0,47 0,48 4,43 4,25 4,1 4,26
(V), 0,0001%
0,80 0,77 0,81 0,79 5,25 5,54 5,13 5,3
(V), 0,00001%
0,84 0,81 0,92 0,85 5,82 6,21 5,96 5,99
(V), 0,000001%
0,54 0,49 0,45 0,49 4,22 4,44 4,75 4,47
(.3), (V) .
-
44
0,0001-0,00001%.
4 .
4
,
3 5 7 9
(2) 34 66 125 162 -
0,005% 33 68 132 174 12
0,00001% 35 68 136 178 16
0,000001%
33 65 128 159 3
1. .. . .: , 1974, .315
2. .., ..
,
//. . . .-
, 1990.-. 55-62.
3. .. . .: , 1976.-.583
4. .. //
. .- .: .- .6.- 1983.- .152-163.
5. 21620-0-76, 21820, 4-76. , , ., 1976. .3-20.
(II) 1/ HNO3 288
.., .., ..
-
Hg(NO3)2--1/ HNO3 288 .
-
45
-
(II) 1 / NO3 288.
- (II) 1 / NO3 288
CHg2+. 10
3 CL
.10
3
E. -lg[L] /
1,98 83,47 80,0 3,29 3,95
2,18 81,84 92,0 3,50 3,61
2,36 80,28 102,0 3,68 3,30
2,604 78,29 113,0 3,88 2,95
2,77 76,86 123,0 4,06 2,73
2,94 75,48 135,0 4,27 2,54
3,10 74,11 145,0 4,45 2,37
3,25 72,87 155,0 4,63 2,23
3,40 71,63 165,0 4,81 2,09
3,54 70,43 177,0 5,02 1,98
3,68 69,27 188,0 5,22 1,87
3,90 67,42 197,0 5,38 1,72
4,11 65,66 206,0 5,55 1,59
4,31 64,00 217,0 5,75 1,48
4,50 62,42 229,0 5,96 1,38
4,68 60,91 239,0 6,14 1,29
4,86 59,48 250,0 6,34 1,22
5,02 58,11 270,0 6,69 1,15
5,18 56,80 277,0 6,82 1,09
5,33 55,55 285,0 6,97 1,04
5,47 54,35 295,0 7,15 0,99
5,61 53,21 306,0 7,34 0,94
5,74 52,11 317,0 7,54 0,90
5,87 51,06 326,0 7,70 0,86
5,99 50,04 337,0 7,90 0,83
6,22 48,14 345,0 8,05 0,77
6,43 46,37 357,0 8,27 0,72
6,63 44,72 365,0 8,41 0,67
6,81 43,19 375,0 8,60 0,63
6,98 41,77 387,0 8,81 0,59
7,22 39,79 390,0 8,88 0,55
-
46
7,44 37,99 394,0 8,96 0,51
7,69 35,84 396,0 9,00 0,46
, n =f(-lg[L]),
1.
. 1. (II) 1 / NO3 288
,
.
pKi (Ki)
: 1=8,97 (K1=9,3108); 2 = 5,72 (K2= 5,210
5); 3 = 4,33 (K3=
2,1104); 4 = 3,58. (K4= 3,8103)
(II)
0,1 / HNO3
.., .., .. -
(II) c 0,1 / HNO3.
lgKi=f(1/) (.)
S ,
. G=H-TS.
-
47
. i (II) 0,1 /HNO3 273-338: 1-1; 2-
2; 3-3; 4-4
(II) 0,1 / HNO3.
(II) 0,1 /HNO3
-,
/
-G,
/
S,
/()
[HgL(H2O)3]2+
27,72 38,02 34,56
[HgL2(H2O)2]2+
16,48 25,49 30,21
[HgL3(H2O)]2+
17,50 19,82 7,73
[HgL4]2+
20,51 15,15 -18,03
(II) (V) 4- -1,2,4 -5 6 / HCL 288
.., .., ..
, - Cu (II) - 4--1,2,4-- 5 6 / HCl 288, , , *i (
*
i ): 1 = 3.75 (1=5,62103); 2 = 3.43
-
48
(2=2,69103); 3 = 3.20 (3=1,5810
3); 4 =3,07(4=1,1710
3).
4--1,2,4- (II) 6 / HCl 288, (V) 4--1,2,4- -5, 6 / HCl 288 1 =
3.35; 2 = 2.79; 3 = 1.81; 4 =1,62. (1=2,2410
3; 2=6,16102; 3=6,410
1; 4=4,2101) ,
i , . , Cu (II) - 4--1,2,4- -5 6 / HCl - 288, 288 (.)
. (II) 4- -1,2,4--5 6 / Cl 288 . 0[u(H2O)6]Cl2;1[uL(H2O)5]Cl2;
2[uL2(H2O)4]Cl2;3
[uL3(H2O)3]Cl2; 4uL4(H2O)2]Cl2
(V) 1--4-
.., ..
, [ReOL2 (OH)2Cl2]2H2O 40
o 80o. 60o. , 1,68% ,
-
49
. , 95 . 2,0% . , [ReOL2(OH)2Cl2]2H2O . 80-156o. 8,40% .
156-292o. 220. 14,28% . , 1--4-. 292-490o . 292-387o , 342o. 18,91%
. 387-490 436. 24,79% 24,79 .
[ReOL(SCN)2Cl]2H2O . ( ) .
- (..), :
E
AR
RT
E
Tn
n
ln)1(
)1(1ln
2
1
n 1,
E
AR
RT
E
Tln
)1ln(ln
2
n = 1,
: T (K); R ; (/); .
-a (..):
2
21
ln1
)1(1ln
ss
s
n
RT
E
RT
E
E
ART
n
n 1,
2)1ln(ln
sRT
E n = 1,
: = - Ts; Ts - .
-
50
(V) 1--4- [ReOL2 (OH)2Cl2]2H2O
, /
, /
G, /
S, /
A, -1
I .. ..
69,66
75,44
66,90
72,68
91,57
91,54
-74,08
-56,64
9,34108
7,76109
II .. ..
73,19
79,38
69,93
76,12
114,21
114,23
-112,68
-96,97
1,05107 7,08107
III
.. ..
84,93
91,92
-80,84
-87,83
-20,95
-34,62
-121,50
-107,94
4,60106 2,34107
IV .. ..
127,87
137,11
122,77
132,01
178,63
179,10
-90,83
-76,57
2,29108
1,35109
V .. ..
221,20
238,39
-215,32
-232,51
-230,87
-264,68
21,94
45,37
2,061014
3,631015
(V) 7 / Br 298
.., .., ..
(V) 12,35 7/ HBr 298 1 -12,35 (V) 7 / HBr 298 .
1
-12,35 (V) 7 / HBr
298
Re(V) 104 L 10
2
E, [L]104 n /
24,7 0,856 24,10 20,38 4,63
30,6 0,849 32,20 15,75 4,19
36,5 0,843 38,60 13,31 3,97
-
51
42,2 0,836 44,40 11,24 3,76
47,9 0,830 49,90 9,57 3,51
53,5 0,824 55,20 8,55 3,32
59,0 0,818 60,00 7,37 3,22
64,5 0,812 64,70 6,23 2,98
69,8 0,806 68,90 5,70 2,60
75,1 0,801 72,30 5,05 2,29
80,3 0,795 75,90 5,00 2,05
90,5 0,784 79,40 4,58 1,76
100,4 0,773 83,00 3,73 1,55
110,0 0,763 86,20 3,46 1,24
121,7 0,750 88,80 3,18 1,03
133,0 0,738 91,00 3,07 0,88
154,6 0,714 92,70 2,85 0,62
174,8 0,692 93,90 2,67 0,47
211,7 0,652 94,80 2,55 0,36
-12,35 (V) 7 / HBr 298 . -12,35 (V) : 1= 3,95;
2 = 3,51; 3 = 3,12; 4 = 2,71; 5=2,15. , .
-
52
1. .., ..
(V)
.2
2. .., .., .., ..,
.. -
3
3. .., .., ..
CHCl3
..4
4. .., .., .., ..
(V) 1--2-
7/ HCl 2735
5. .., ..
(V) 8
6. .., .., .., ..,
.. (III)
, ,
( ) ,
9
7. .., .., .., ..
-
10
8. Gouda G.A., Aminjanov A.A. Potentiometric and
thermodynamic
investigation of rhenium(V) complexes with
4,5-dihydro-1H-imidazole-2-
thiol...12
9. .., ..
(CnH2n+1)4NReO4 (1
-
53
10. .., .., ..
(V) 1--2-
4,5 / HCl 298 21
11. . ., .., ..
...22
12. .., .., .., ..
,
23
13. .., .., .., ..
.25
14. .., .., .., ..,
..
(V) (V)
...26
15. .., ..
(II) 3--1,2,4--5
6 / l 273.28
16. .., .., ..
-30
17. .,. .., .., .
(V) (II) c 1--2,3-
-5- 6 / l 318 ...31
18. ..
(N--
)32
19. .., .., .., ...
(+4)
33
-
54
20. .., .., .., ..,
.. L+2.18%Fe,
0,03% NaCl35
21. .., .., ..
4-
1,2,4- (II) 6 / HCl....36
22. .., .., .., ..,
.. Al+2.18%Fe,
3%- NaCl37
23. .., .., ..,
.. (III) (V) c 1--2,3-
-5- 6 / I 30838
24. .., .. VO3+
-
VO2+
/VO3+
39
25. .., .., .. ..
(V) [ReOL4Br]Br22H2O
41
26. .., .., ..
(II)
1 / NO3 288.44
27. .., .., ..
(II) 1 / HNO3..46
28. .., .., ..
(II) (V) 4- -1,2,4
-5 6 / HCl 288 .....................................47
29. .., ..
(V) 1--4-
..48
30. .., .., ..
(V) 7 / Br
298 50