-

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: ggouda1973@yahoo.com

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.

REFERENCES

1. Andres Garcia E. and Blanco Gomis D., Microchem. Acta, 1996, 4, 124. 2. Cao S. and Zhang M., J. Trace Microprobe Tech., 1999, 17, 157. 3. Bjerrum J., Metal amine formation in aqueous solutions: theory of the reversible step

reactions, Haase P. and Sons (Copenhagen, Denmark), 1941, 296.

4. Florence A.T. and Attwood D., Physical principles of pharmacy, Macmillan (London), 1981.

5. Poddar S.N., Dey K. and Poddar N.G., Indian J. Chem., 1970, 8, 364. 6. Schwarzenbach G. and Ackerman H., Helv. Chim. Acta, 1948, 31, 1029. 7. Pund D.A., Bhagwatkar R.A., Tayade D.T. and Rathod D.B., Rasayan J. Chem., 2010,

3(2), 246.

8. Tihile M.S., Journal of Chemical and Pharmaceutical Research, 2012, 4(4), 2223. 9. Dipak T.T., International Journal of Chemistry, 2011, 3(1), 36. 10. Gudadhe S., Narwade M.L. and Jamode V.S., Acta Ciencia Indica (Chem.), 1985, 11, 234. 11. Saha N., Dalia M. and Sinha S., Indian J. Chem., 1986, 25A, 629. 12. Rana A.K. and Shah J.R., J. Indian Chem. Soc., 1986, 63, 281. 13. Fukuda V., Morishita R. and Sone K., Bull. Chem. Sep. Jpn., 1985, 49, 1017. 14. Jolly V.S., Arora G.D. and Taiwar P., J. Indian Chem. Soc., 1990, 61, 1001. 15. Natrajan C. and Thormaraj P., Indian J. Chem., 1991, 30A, 722. 16. Narwade M.L., Chincholkar M.M. and Sathe S.W., J. Indian Chem. Soc., 1985, 62, 194. 17. Sawalakhe P.D. and Narwade M.L., J. Indian Chem. Soc., 1995, 70, 25. 18. Kadu M.V. and Jamode V.S., Asian J. Chem., 1999, 11, 420. 19. Hamid R.J. and Hadi n.Z., E-Journal of Chemistry, 2012, 9(3), p. 1518-1525. 20. Bjerrum J. and Bang E., Acta Chem. Scand. Ser., 1979, A33, 297. 21. Irving H.M. and Rossotti H.S., J. Chem. Soc., 1953, 3397; J. Chem. Soc., 1954, 2904.

22. Valeria M. Nurchi, Guido Crisponi, Tiziana Pivetta, Martina Donatoni and Maurizio Remelli, J. of Inorg. Biochem., 2008, 102(4), 684.

23. Atkins, Peter; De Paula, Julio (10 March 2006). Physical Chemistry (8th ed.). Freeman W.H. and Company, p. 212.

24. Ives D.J.G., Chemical Thermodynamics, University Chemistry, Macdonald Technical and Scientific, 1971.

25. Rigano C., Rizzarelli E. and Sammartano S., Thermochim. Acta, 1979, 33, 211. 26. Abd Erbary H.M., Shehata H.A., El Arab M.A.F., Mohamed A.A. and Emara M.M., J. Ind.

Chem. Soc., 1996, 73, 25.

27. Nair U.S.A. and Nancollas G.H., J. Chem. Soc., 1961, 255, 4367.

19

28. Dickerson R.E., Geis I. and Benjamin I.W.A., Chemistry, Matter and the Universe, (USA), 1976.

29. Amindzhanov A.A. and Kurbanov N.M., Journal of Inorganic Chemistry (Russian Federation), 1990, 35(3), p. 672-678.

30. Promila D.T. and Lonibala R., J. Chem. Eng. Data, 2010, 55, 1166. 31. Amindzhanov A.A. and Gagieva S.Ch., Journal of Inorganic Chemistry (Russian

Federation ), 1996, 35(3), p. 1867-1871. 32. Amindzhanov A.A., Akhmedov K.U. and Kotegov K.V., Journal of Inorganic Chemistry

(Russian Federation ), 1988, 33(2), p. 379-384.

(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:

harin-ei@mail.ru

, , , . , 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. alakaeva-L@mail.ru

- .

. . , 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 "-

", , , iitcm@yandex.ru

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