CC BY
17
UDC 541.49:544.35
COMPLEXES OF RARE EARTH METALS WITH 1,2-BENZENE DICARBOXYLIC (o-PHTHALIC) ACID
M.K.Munshiyeva, B.T.Usubaliyev*, F.B.Aliyeva, S.R.Mamedova, F.F.Jalaladdinov
M.Nagiyev Institute of Catalysis and Inorganic Chemistry, NAS of Azerbaijan
*
Scientific research institute "Geotechnological problems of oil, gas and chemistry "under
State University of Oil and Industry
Received 04.04.2016
The new synthesized complexes of neodimium, samarium and gadolinium with o-phthalic acid were studied by X-ray, DTA and IR spectroscopic analysis methods. Clathrate compounds were obtained on the basis of these complexes. Formic acid (for samarium complexes) and the acetic acid (for gadolinium complexes) were chosen as "guest" molecules. According to X-ray, elemental, IR spectroscopic and deriva-tographic analyses the identity of complexes and clathrates on their basis, form of coordination of o-phthalic acid, existence and amount of "guest" molecules in a clathrate, as well as processes of thermal decomposition and formation of supramolecular compounds: {Sm2[C<;H4(COO)2]3-2H2O}3HCOOH and {Gd2[C6H4(COO)2k5H2O}-2CH3COOH were established.
Keywords: complexes, lanthanides, o-phthalic acid, clathrates, supramolecular compounds.
Part I. Synthesis and structural-chemical investigation of neodimium, samarium and gadolinium complexes with o-phthalic acid
There are considerable works dedicated to synthesis and study of structure and properties of complexes of mono- and polybasic aromatic carboxylic acids with metals in literature. The coordination compounds of transition metals with monocarboxylic acids (benzoic acid and its derivatives) are of great importance [1, 2] among them. Study of crystalline structure allows us to choose these compounds as initial complexes to form clathrate compounds.
It was established [2, 3] that clathrates have been formed on the basis of complexes with dimeric and polymeric structures.
Monocarboxylic acids were used in obtaining of rare earth metals (REM) complexes [4-7]. These complexes are efficient materials for liquid lasers, catalysts, anticoagulant of blood, reagents and active agents which influence on various biochemical processes.
Complexes of REM with benzoic acid and its derivatives have been widely studied. The research of known structural properties of REM complexes with monocarboxylic aromatic acids shows the possibility of formation of their
complexes with bicarboxylic aromatic acids -phthalic acid and its isomer. We propose that flaky character of these acids and their ability to form such kind of structures with REM is promising for complex and inclusion-clathrate compounds formation. These researches have been carried out for the first time.
Phthalates of REM were synthesized by exchange reaction of corresponding soluble salts of the indicated metals salts and sodium phthalate obtained by interaction of o-phthalic acid and sodium hydroxide. The main facfor which influences on the formation of these complexes is pH value of solution which must be equal to 6.5 [8, 9].
When mixing water solutions of sodium phthalate and chlorides or nitrates of REM taken at the ratio 3:2 and slightly heated, the formation of thick flaky coloured mass according to of these metals cations was observed. After some minutes the solution was filtered, the product was washed by distilled water and dried at room temperature (Table 1).
Obtained complexes were studied by the methods of X-ray phase (DRON-3.0, Cu^-ra-dion, Ni-filter), thermographic (Derivatograph Q-1500 Paulic-Paulic-Ardey, sample amount - 640 mg, heating rate - 100/min, sensibility - 500 mV, standartd - Al2O3) analyses. Element composition
of the product was determined by the method of chromatography (Analizer CHNSO "E" Carlo ERBA). The metal content was found on the basis of oxide amount obtained after heating the sample till 10000C on derivatography from the curve of mass loss. IR spectra were registered on SPEC0RD-M-80 at the interval of 400-4000 cm-1.
Water content was not calculated.
With the aim of obtaining homogenity and isostructurality depending on the order number of complex-forming agent the crystals were studied by X-ray phase method. The data of interplanar distances (d, A), final product and initial phthalic acid relative intensities (///o) of diffraction lines show that X-ray-graphic data of products and corresponding initial components were completely different (Table 2).
Therefore, obtained complexes are not isostructural, i.e. depending on atomic mass of relative elements the structures of complexes which changed in spite of all three elements (Nd, Sm, Gd) are in the same rare earth metals serium subgroup. However, the conformity of some lines data of obtained complexes shows the presence of common structural units and motives in their crystalline structures.
By IR spectroscopy the coordination of C6H4(C00) and presence of water molecules in a form of OH- or HOH groups were determined (Figure 1).
On IR spectra of REM complexes with phthalic acid two similar groups of bands caused by the vibration of water molecules and carboxylic group were observed.
Table 1. Elemental analysis of formed crystals
Formulae Calculated, mas. % Found, mas. %
Me C H O Me C H O
Nd2C24H12O12 36.95 36.92 1.53 24.61 37.14 36.87 1.49 24.50
Sm2C24Hi2Oi2 37.87 36.36 1.51 24.27 37.62 36.57 1.72 24.10
Gd2C24H12O12 38.95 35.75 1.48 23.82 38.49 35.91 1.51 24.00
Phthalic acid Nd-phthalate Sm-phthalate Gd-phthalate
d, Â I/I0 d, Â I/I0 d, Â I/I0 d, Â I/I0
7.138 3 14.26 100 16.13 100 11.05 100
5.731 48 10.65 28 10.33 20 9.33 32
4.821 38 9.43 8 9.03 12 7.13 8
4.197 100 7.21 12 6.59 4 5.90 24
3.993 19 6.35 4 5.18 4 5.54 28
3.597 100 5.75 4 5.19 4 5.01 8
3.343 40 4.24 20 4.80 4 4.67 20
3.302 65 5.17 12 4.01 12 4.33 8
2.927 15 3.94 16 3.43 4 4.19 4
2.651 6 3.83 4 3.36 4 3.68 16
2.525 6 3.72 4 3.28 4 3.28 8
2.438 20 3.49 8 3.15 32 3.16 16
2.393 100 3.14 4 2.91 4 2.95 4
2.261 5 280 4 2.78 4 2.76 4
2.138 5 2.68 4 2.64 4 2.66 12
2.088 5 2.62 4 2.39 4 2.57 4
1.895 10 2.54 8 2.34 4 2.39 4
2.36 4 2.21 12 2.24 4
2.23 4 2.07 4 2.10 4
2.17 4 1.99 4 2.03 4
1.72 4 1.82 8 1.94 4
1.66 4 1.77 4 1.89 8
1.59 4 1.57 4 1.87 4
1.78 4
1.66 4
Table 2. Data of X-ray graphic analysis of initial acid and obtained complexes
4000
Fig. 1. IR spectra of complex compounds: 1 - neodimium phthalate, 2 - samarium phthalate, 3 - gadolinium phthalate.
This fact was easily interpreted at the comparable study of IR spectra of phthalic acid and carboxylate. On the spectra of complexes absorption band of nonionized carboxylic qroups COOH at 1720-1700 cm-1 was not observed. Instead of this absorption bands at 1552 cm-1 (for Nd and Sm phthalates) and at 1548 cm-1 (for Gd-phthalate) typical for nonsymmetric and symmetric valent vibration of acid carboxylic residue were observed. Also it was observed that these bands shift to the low-frequency region more strongly than in complexes of monobasic aromatic acids. This fact testifies to that both hydrogen atoms of carboxylic groups in phthalic acid are substituted with REM atoms and shows stronger interaction between REM and ligand (M - L) in complexes of bicarboxylic acids, thus the formation of complexes results in the dissosia-tion of carboxylic groups and appearance of COO- ions. Herewith the resonance between the C=O and C-O bonds is possible [10, 11].
On IR spectra of neodimium and samarium phthalates the bands at 1620-1610 cm-1 belonging to the deformation vibration of water 5 (HOH) which confirms the presence of crystallization water, were observed. This band is absent on IR spectra of gadolinium phthalate that testifies to the absence of crystallization water in this complex and apparently is convected with the special position of gadolinium among lanthanides. Being the seventh element in the
raw of lanthanides, gadolinium and all of its ion w-sublevels are half filled and this leads to the strengthening of electronic bond in the atomic sheets. For this reason gadolinium behaves differently as compared with other lanthanides in complexation and forms nonhydrate complex with phthalic acid.
So the formation possibility of complex compounds of neodimium, samarium and gadolinium with o-phthalic acid was proved and the chemical formula of obtained product was determined.
The clear endothermic effect with maximum at 2480C corresponding to the removal of 13.4% of water is observed on DTA curves of neodimum phthalate (Figure 2). This mass loss is equal to 7 molecules of water, i.e. all of water molecules are removed in one stage which is connected apparently with the nearness of their crystallographic position in structure. After this the deep step, probably connected with the formation of stable intermediate product, is observed. Destruction and burning of organic residue of neodimium phthalate complex with corresponding endo- and exothermic effects in a wide temperature range of 410-8750C and the formation of final product Nd2O3 take place. Total mass loss equals to 59.5%.
As is seen from derivatographic analysis of samarium phthalate (Figure 3) its dehydration begins at ~100°C and proceeds in one stage as in neodimium complex.
TG DTA
T
Fig.2
Fig.3. Derivatograph data of samarium phthalate.
59.5%
. Derivatograph data of neodymium phthalate.
The removal of hydrate residue of complex is achieved till 1650C, corresponding to removal of two water molecules, endothermic effect with maximum at 1280C is observed on DTA curve. The mass loss is equal to 4.6%. Decomposition of samarium phthalate is accompanied by endothermic effect with maximum at 2020C and 8.7% mass loss is found at this time. Then the step confirming the formation of intermediate compound which is stable until ~400°C is determined. Then the destruction of this compound and burning of organic residue occur. The process is accompanied by the corresponding endo- and exothermic effects, probably, at this time samarium carbonate is formed and at high temperature the latter is converted into the samarium dioxymonocarbonate:
Sm2(CÜ3)3 ^ Sm2O2CÜ3 + 2CO2.
The formation of samarium dioxymono-carbonate is proved by the X-ray analysis. Next endothermic effect with maximum at 7820C is corresponded to the decomposition of this product and formation of Sm2O3. Total mass loss is equal to 57.5%.
The derivatographic data of gadolinium phthalate is characterized by some endo- and exothermic effects. It is established that the first deep clear endothermic effect (Figure 4) with maximum at 1920C corresponds to the removal of crystallization water.
The mass loss is equal to 9.6%. About 0.8% of hydroscopic water is removed till 1050C. Decomposition of complex proceeds at 2880C and 16% of organic rest of complex is removed. Further processes of decomposition, burning and destruction of carbonate proceed at the temperature interval of 314-8540C. At the last endothermic effect with maximum at 8540C the formation of Gd2O3 as a final product of thermolysis is observed. The total mass loss of the entire process is equal to 60.4%. This amount corresponds to the removal of 5H2O moles and 3C6H4(COO)22-. At the end of thermolysis of neodimium, samarium and gadolinium complexes the residual mass amount according to the TG curves is equal to 40.5, 42.5 and 39.6% which corresponds to the final products: Nd2O3, Sm2O3, Gd2O3.
Fig. 4. Derivatograph data of gadolinium phthalate.
Thus, on the basis of carried out investigations more precise chemical compositions of synthesized products are made:
Nd2[C6H4(COO)2]3-7H2O, Sm2[C6H4(COO)2]3-2H2O, Gd2[C6H4(COO)2]3-5H2O.
Obtained 5H2O moles in gadolinium complex refuses the above-mentioned assumption on absence of crystallization water in its structure [12, 13].
Part II. Study of clathrate forming ability of samarium and gadolinium complexes with o-phthalic acid
REM with benzoic acid and its derivatives form some complexes of isostructural groups: dimeric, tetrameric, polymeric chain structures. It is proposed that crystallization of such complexes is connected with the order of filling and lanthanide compression [12, 13]. Monocarbox-ylic benzoic acid and its derivatives form the complexes with REM and some of these complexes have flaky structure, therefore they can be considered as clathrate forming complexes. In
this term the bicarboxylic aromatic acids have special place due to their flaky structure, so these investigations are very interesting. The aim of the present paper is to realize the possibility of preparation of new synthesized clathrate compounds on the basis of samarium (III) complex. By physico-chemical methods the chemical formula of Sm2[C6H4(COO)2]r2H2O complex was established (see Part 1) and the formic acid is selected as a "guest" molecule. With the aim of clathrate formation based on this complex, it was dissolved in formic acid with heating. During cooling to ambient temperature the straw poly-crystalline powder falls out. The crystals were washed out by distilled water, dried on filter and studied by X-ray, thermographic, IR spectro-scopic and element al methods.
The results of elemental analysis of both samples (Table 3) are agree well with calculated data. X-ray analysis confirms idendity of synthesized compounds. The values of interplanar spacing and intensity of diffraction lines of used acid, initial complex and obtained clathrate are given in Table 4.
Table 3. Data of elemental analysis of complex Sm2[C6H4(COO)2]3 and its clathrate with HCOOH
Found, % Formula Calculated, %
Sm C H O Sm C H O
35.99 34.85 1.98 27.12 Sm2C24H16O14 36.23 37.78 1.93 24.06
30.28 32.98 2.31 34.43 Sm2C27H22O20 31.10 33.51 2.27 33.12
Table 4. X-ray data of o-phthalic acid, initial Sm complex and its clathrate with HCOOH
C6H4(COOH)2 Sm2(C6H4(COO)2)3-2H2O [Sm2(C6H4(COO)2)3-2H2O]-3HCOOH
d, Â I/I0 d, Â I/I0 d, Â I/I0
7.138 3 13.556 16 14.118 43
5.731 48 6.916 6 10.45 7
4.821 38 5.659 9 9.29 5
4.197 100 5.215 100 7.25 5
3.993 19 4.755 17 5.75 7
3.507 100 4.152 17 5.295 100
3.343 40 3.948 7 4.77 14
3.302 65 3.647 8 3.69 23
2.927 15 3.479 6 3.48 10
2.651 6 3.264 46 3.30 6
2.525 6 3.151 9 3.16 80
2.438 20 3.012 9.5 3.02 43
2.383 100 2.916 7 2.65 8
2.261 3 2.606 37 2.39 29
2.138 3 2.226 6 2.23 10
2.088 5 2.131 7 1.99 6
1.895 10 1.979 7 1.85 6
1.876 7 1.75 6
Table 5. Results of thermogravimetric analysis of Sm2|C6H4(COO)2|y2H 2O and its clathrate with HCOOH
Decomposition stage Temperature interval, 0C T C0 ■L max ^ Mass loss, %
found calculated
I. Sm2(C6H4(COO)2)3-2H2O 100- -165 132 4.6 4.65
Beginning of decomposition Sm2(C6H4(COO)2)3 165- 200 174 42.8 45.1
Forming Sm2O3 >780
II. {Sm2(C6H4(COO)2)3-2H2O}3HCOOH
-3HCOOH 170- -231 198 14.8 14.3
-2H2O 231- 252 235 3.54 3.72
Decomposition and burning out of organic part 262- 800 640 45.02 45.93
Forming Sm2O3 >780 36.07 38.2
Comparison of interplanar space values of initial Sm complex and its clathrate shows that in clathrate this parameter is longer, i.e. during clathrate formation some parameters of unit cell increase. The presence of coordinating water molecules as well as the type of coordination of C6H4(COO) and HCOOH was confirmed by IR spectroscopic method. On IR spectra of initial complex and its clathrate broad bands appear at 3400-3380 cm-1 and 1020, 900, 890, 870 cm-1 typical for crystal and coordination water correspondingly. The comparison of thermogram of initial complex Sm2[C6H4(COO)2]3-2H2O and its clathrate with formic acid demonstrates the clear distinction in dehydratation temperature.
As is seen in Table 5 dehydratation of clathrate occurs at higher temperature in com-parision with the initial complex. At once after elimination of "guest" molecules the initial structure of complex is recovered. Probably the inclusion of formic acid as "guest" molecule in crys-tallographic cell of an initial complex makes it close-packed lattice and subsequently, stable one. This result can be used for preparation of thermostable complex of aromatic carboxylic acids with metals. It should be noted that this doesn't restrict the preparation of thermostable structures, it may vary by fitting appropriate "guest" molecules. According to the results of investigations the chemical content and formula of obtained new clathrate compound were determined as Sm2[C6H4(COO)2k2H2O-3HCOOH. During the formation of clathrate compound due to inherited from phthalic acid flaky structure the intermolecular distances of polymeric layer of initial complex increase and form intermolecular channels that can capture "guest" molecules, appropriate in term of crystal chemical
and geometrical features. The clathrate compound Sm2[C6H4(COO)2]3-2H2O-3HCOOH consists of infinite dimeric chains compound Sm2[C6H4(COO)2]3-2H2O in which two phtalate anions are in equatorial position, forming two infinite-connected chains, where as the third coordinated phthalate anion is in axial position and forms the bridge between chains. The other axial positions are taken by two water molecules. Such infinite dimeric chain is the structural unit of compound. These coordinated water molecules join the dimeric chains to each other by forming hydrogen bonding with "guest" molecules of formic acid. It leads to formation of supramolecular structure. The third molecule of formic acid is supposed to be between the layers by hydrogen bonding with coordinated water molecules. Thus, in initial complex and clathrate samarium contains octahedral configuration with four oxygens of two carboxylates of phthalic acid in equatorial positions, one oxygen of carboxylate of third phthalic acid and one oxygen of water molecule in axial position as it is shown below on the proposed scheme of Sm2[C6H4(COO)2]32H2O formation:
COMPLEXES OF RARE EARTH METALS WITH 1,2-BENZENE DICARBOXYLIC 137 Table 6. Elemental composition of obtained compounds_
№ Found, % Formula Calculated, %
Sm C H O Sm C H O
I 34.82 31.91 2.52 30.75 Gd2C24H22O]7 35.08 32.13 2.45 30.17
II 31.92 34.02 2.81 31.25 Gd2C20H30O21 32.08 34.27 2.65 31.00
Table 7. X-ray data of initial Cd complex and its clathrate with CH3COOH
Gd2[C6H4(COO)2]3-5H2O Gd2[C6H4(COO)2]s-5H2O-2CH3COOH
d, Â I/I0 d, Â I/I0
11.051 100 13.810 100
9.329 37 10.210 10
7.126 8 9.408 8
5.906 30 8.898 8
5.539 30 8.299 6
5.000 8 7.858 4
4.671 21 7.184 8
4.332 11 6.959 10
4.187 6 6.647 6
3.578 16 5.680 4
3.280 12 5.321 4
3.156 21 5.120 4
2.845 7 4.622 10
2.661 13 4.179 21
2.571 7 4.040 6
2.387 8 3.760 6
2.232 12 3.610 5
2.100 6 3.437 4
2.033 8 3.290 35
1.895 13 3.142 38
1.865 6 2.797 6
1.843 7 2.775 6
1.781 7 2.714 7
1.687 8 2.373 6
1.652 8 2.219 9
As is shown earlier gadolinium (III) with o-phtalic acid forms the complex of chemical formula Gd2[C6H4(COO)2]3-5H2O. For formation of a clathrate this complex was dissolved in acetic acid by slight heating. The hot solution was filtered and left for crystallization. After cooling and evaporation the deposits of small needle transparent crystals were observed. Crystals were washed by distilled water and dried at 300C.
Elemental analysis is given at the Table 6.
X-ray graphic data of initial complex and clathrate on its basis are given in Table 7.
The comparison of these data shows that the most intensive maximum at 80 in initial complex moves to low angle region 6.400 in clathrate and the interplanar distance increases from 11.051 A to 13.810 A, i.e. one of the pa-
rameters of crystal carcass increases during clathrate formation. On X-ray data maximums were observed for the whole of diffractograph data. It confirms the high symmetry of crystals.
IR spectroscopic study of these complexes revealed the presence of three groups of adsorption bands at 1560, 1408, 1440 and 1640, 1448 cm-1 which are related to the asymmetric and symmetric absorption bands of carboxylic groups of phthalic acid. It shows their various coordination forms with central atom. Unlike initial complex on IR spectra of clathrate the new absorption bands, which are related to asymmetric (A,as) and valent symmetric (ks) vibrations of carboxyl group of acetic acid, appear at 1720 and 1336 cm- . This fact shows the noncoordination of acetic acid with central atom. Besides these adsorption bands there are the
bands at 3600-3000 cm-1 and clear band at 1650 cm-1, which are related to valent and deformation vibrations of OH-group and H2O molecules. The appearance of same groups of absorption at 1560, 1408 sm-1, 1616, 1440 sm-1, 1640, 1448 sm-1 which are related to asymmetric (^as) and symmetric (A,s) adsorption bands of phthalic acid carboxylic groups, shows that the main structure motive of complex remains at clathrate formation and, as is seen in Table 7, the results of X-ray analysis data of both complexes conform very well.
Thermographic research of clathrate (Table 8) shows that in temperature range of 59-1450C deep and unclear endothermic effect with maximum is observed at 1000C on DTA curve of heating. The mass loss accompanied by this endothermic effect is equal to 0.8% (experimental) and 0.9% (calculated), i.e. the loss of
0.5 mol. of water takes place. At higher temperature (145-2100C) the second endothermic effect with maximum at 1800C, belonging to the loss of 2.5 mol of water, is observed. The mass loss at this time is equal to 4.7% (calculated 4.6%). The third endothermic effect with maximum at 2470C is observed at the temperature interval of 210-2590C i.e. the loss of acetic acid molecules occurs and the mass loss is equal to 11.7% (calculated 12.2%). Then at the temperature interval of 259-10000C the decomposition of arid complex occurs; the mass loss is equal to 44.1% (experimental) and 45.0% (calculated)
1.e. the burning of organic rest takes place. The
final product of thermolysis is Gd2O3. These analysis allowed us to determine the chemical formula of clathrate {Gd2[C6H4(COO)2]3 -5H2O}-2CH3COOH. The mass loss of gadolinium oxide is 38.7% (calculated - 36.9%).
The thermographic research of initial complex and its clathrate shows that their thermal stability and thermal decomposition di-rectrions change depending on the "guest" molecules, i.e. firstly, the temperature of water removal in clathrate (500c) is lower by 230C (730C for complex), secondly, unlike the complex there is a stable phase at 288-3140C on thermographic data of clathrate.
The proposed schematic structure of clathrate can be shown by the following way: this structure consists of double polymeric chains which are the structural unit of clathrate. The double polymeric chain is obtained on the basis of monomer polymeric chains formed at the coordination of metals with two phthalic acid anions. The third anion forms a bridge between the polymeric chains, other coordinations are filled by the water molecules. There is a cross-linking of the double chains due to acetic acid molecules which as "guest" molecules are situated between the double chains and form hydride bond with the coordination water molecules and are the bridge between the double polymeric chains. So, the supramolecular compound {Gd2[C6H4(COO)2]3-5H2O-3CH3COOH} is formed.
Compound AT 0P AT endo? C AT 0C t-*1 max? ^ AT 0C t-*1 exo? ^ AT 0C t-*1 max? ^ Am, % Common composition
found calculated
1 73-130 130-288 105 192 192-948 314 424 474 600 948 1.8 8.6 51.1 38.5 2.0 8.3 49.52 40.43 -H2O -4H2O C6H4(COO)2 Gd2O3
2 50-145 100 0.8 0.9 -0.5 H2O
145-210 180 380 4.7 4.6 -2.5 H2O
210-259 247 259-1000 455 11.7 12.2 2CH3COOH
590
672 44.1 45.0 C6H4(COO)2
870
38.7 36.9 Gd2O3
Table 8. The main thermographic data of complex Gd2[C6H4(COO)2]3-5H2O (1) and its clathrate with CH3COOH (2)
References
1. Порай-Кощиц М.А. Кристаллохимия и стереохимия одноосновных карбоксилатов переходных металлов // Журн. структ. химии. 1980. Т. 21. № 3. С. 146-180.
2. Ашурова С.А. Дисс. ... канд. хим. наук. Баку: ИНФХ АН Азербайджана. 1999. 133 с.
3. Абдурахманова П.С., Усубалиев Б.Т., Мунши-ева М.К., Ганбаров Д.М. Синтез и кристаллическая структура клатратного соединения Zn(C6H5COO)2-2H2O-2CH3COOH // Коорд. химия. 2010. Т. 36. № 10. С. 802-806.
4. Хиялов М.С. Дисс. ... канд. хим. наук. Тбилиси: Тбилисск. гос. ун-т. 1983. 199 с.
5. Хиялов М.С., Амирасланов И.Р., Мамедов Х.С., Мовсумов Э.М. Кристаллическая и молекулярная структура и-аминобензоата неодима(Ш) // Журн. структ. химии. 1981. Т. 22. № 3. С. 113-119.
6. Хиялов М.С., Амирасланов И.Р., Мамедов Х.С., Мовсумов Э.М. Кристаллическая и молекулярная структура n-аминобензоата диспрозия(Ш) // Коорд. химия. 1981. Т. 7. № 3. С. 445-449.
7. Ефремова Г.И., Бучкова Р.Т., Лапичкая А.В., Апркес С.Б. Термографическое и ИК-спектро-
скопическое исследование и-аминобензоатов РЗЭ // Коорд. химия. 1977. Т. 22. № 4. С. 948-953.
8. Гостинцев В.В., Вальцев В.К., Балашевский Г.Ф. Синтез и исследование основных бензоа-тов редкоземельных элементов // Журн. неорг. химии. 1976. Т. 21. № 8. С. 2030-2034.
9. Ефремова Г.И., Бучкова Р.Т., Лапичкая А.В., Апркес С.Б. Термографическое и ИК-спектроскопическое исследование и-аминобензоатов РЗЭ // Коорд. химия. 1977. Т. 3. № 8. С. 1184-1188.
10. Беллами Л. Новые данные по ИК-спектрам сложных молекул. М.: Мир, 1971. 505 с.
11. Накамото К. ИК-спектры и спектры КР неорганических и координационных соединений. М.: Мир, 1991. 318 с.
12. Муншиева М.К., Джалаладдинов Ф.Ф., Ганбаров Д.М. Получение и структурно-химическое исследование комплексов неодима, самария и гадолиния с о-фталевой кислотой // Азерб. хим. журн. 2011. № 4. С. 42-45.
13. Ганбаров Д.М., Мамедова С.Р., Усубалиев Б.Т., Джалаладдинов Ф.Ф., Муншиева М.К. Синтез и уточнение химических составов гидратов Ln2[C6H4(COO)2]3-XH2O // Азерб. хим. журн. 2012. № 4. С. 99-102.
NADiR TORPAQ ELEMENTLORiNiN 1,2-BENZOLDiKARBON (o-FTAL) TUR§USU iLO KOMPLEKSLORI
M.K.Mun$iyeva, B.T.Usubaliyev, F.B.Oliyeva, S.RMammadova, F.F.Calabddinov
Yeni sintez olunmu§ neodim, samarium va qadoliniumun o-ftal tur§usu ila komplekslari rentgenoqrafik, derivatoqrafik va iQ spektroskopik analiz usullari ila tadqiq edilmi§dir. Onlarin asasinda klatrat birla§malar alinmi§dir. "Qonaq" molekullari kimi qan§qa tur§usu (samarium kompleks ugun), sirka tur§usu (qadolinium kompleksi ugun) segilmi§dir. Rentgenoqrafik, element, iQ spektroskopik analiz usullan ila komplekslarin va onlarin asasinda klatratlarin eyniliyi, o-ftal tur§usunun koordinasiyasi "qonaq" molekullarin movcudlugu va miqdari, termiki pargalanma proseslari, supramolekulyar birla§malar {Sm2[C6H4(COO)2]3-2H2O}-3HCOOH va {Gd2[C6H4(COO)2]3-5H2O}-2CH3COOH amala galmasi tasdiq edilmi§dir.
Agar sozlar: kompleksbr, lantanoidbr, o-ftal tur§usu, klatratlar, supramolekulyar birb§m3hr.
КОМПЛЕКСЫ РЕДКОЗЕМЕЛЬНЫХ ЭЛЕМЕНТОВ С 1,2-БЕНЗОЛДИКАРБОНОВОЙ
(о-ФТАЛЕВОЙ) КИСЛОТОЙ
М.К.Муншиева, Б.Т.Усубалиев, Ф.Б.Алиева, С.Р.Мамедова, Ф.Ф.Джалаладдинов
Вновь синтезированные комплексы неодима, самария и гадолиния с о-фталевой кислотой были изучены методами рентгенографического, дериватографического и ИК-спектроскопического анализа. На основе этих комплексов были получены клатратные соединения. В качестве "гостевых" молекул были выбраны муравьиная (для комплексов самария) и уксусная (для комплексов гадолиния) кислоты. По данным рентгенографического, элементного, ИК-спектроскопического методов анализа установлены идентичность комплексов и клатратов на их основе, форма координации о-фталевой кислоты, наличие и количество "гостевых" молекул в клатрате, а также процессы термического разложения и формирования супрамолекулярных соединений {Sm2[C<;H4(COO)2]3-2H2O}-3HCOOH и {Gd2[C6H4(COO)2]3-5H2O}-2CH3COOH.
Ключевые слова: комплексы, лантаниды, о-фталевая кислота, клатраты, супрамолекулярные соединения.
