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23
Isakov Hayatulla,
candidate of technical sciences, assistant professor of the Department of Chemistry, Andijan State University
Uzbekistan, Andijan, E-mail: xayotilla.isakov@bk.ru
ABOUT COORDINATED COMPOUNDS OF ACETATES OF DIVALENT CO, CU AND ZN WITH FURFURYLDICARBAMIDE
Abstract: In this paper, the results are presented by synthesizing the study of complex compounds of divalent cobalt acetate, copper and zinc with furfuryldicarbamide.
Keywords: furfuryldicarbamide, metal acetates, furfural, IR spectrum, complex compounds, derivatogram, thermolysis, thermal effect.
Numerous studies in the literature have been devoted to the synthesis and study of the properties of coordination compounds of various metal salts with carbamide and its derivatives [1; 2]. Coordination of the apical ligands is in many cases carried out through the oxygen atom of the carbonyl group. The furfuryl- dicarbamide molecule contains 7 donor atoms - three oxygen atoms and four nitrogen atoms of primary, secondary amine groups and can form complexes, with metal salts exhibiting a competitive ability for coordination of the metal with acidoligands and water molecules [3].
Objects and methods of research
This report describes the results of the synthesis and study of the physicochemical properties of coordination compounds of acetates of bivalent cobalt, copper and zinc with furfuryl dicarbamide (L).
Synthesis of coordination compounds was carried out by the interaction of saturated aqueous solutions of the corresponding metal acetates and furfury ldicarbamide in a molar ratio I: I with subsequent precipitation of powder precipitates.
Analysis of synthesized compounds on the content of metals was carried out according to [4], nitrogen by micromethod DUMA [5], carbon and hydrogen by burning in an oxygen current.
To establish the individuality of the complexes, radiographs were taken on a DRON-2 installation with a C-antikatode [6].
IR absorption spectra of furfuryldicarbamide and the resulting compounds in the 400-4000 cm-1 region were recorded on an IR-Fourier spectrophotometer system 2000, firm Perkin Elmer using the method of pressing samples with KBr.
The thermal analysis was carried out on a de-rivatograph of the Paulik-Paulik-Erdei system, at a rate of 10 deg / min with a 0.1 g sample with a sensitivity of T-900, TT-100, DTA-1/10, and DTG -1/10 galvanometers. The holder was a platinum crucible with a diameter of 7 mm without a cover. Al2O3 was used as a reference.
Results and their discussion
The results of the elemental analysis of complex compounds are given in (Table 1).
Table 1.- Results of elemental analysis
Compound M% N% C% H%
Found Calcu. Found Calcu. Found Calcu. Found Calcu.
1 2 3 4 5 6 7 8 9
Furfuryldicarbamide (L) - - 28.41 28.28 42.53 42.42 5.11 5.05
1 2 3 4 5 6 7 8 9
Co(CH3COO)2-L-3H2O 13.69 13.77 12.95 13.08 31.03 30.84 5.16 5.14
Cu(CH3COO),.L.H2O 16.04 15.97 13.99 14.07 33.40 33.17 4.39 4.52
Zn(CH3COO)2-L-2H2O 15.80 15.68 13.51 13.43 31.70 31.65 4.77 4.84
Comparison of X-ray diffraction patterns of compounds shows that they differ from those of the initial metal acetates and furfuryldicarbamide, therefore, the complexes have individual crystal structures.
Some vibrational frequencies in the IR absorption spectra of the uncoordinated furfuryldi-carbamide molecule and its complexes with Co (II), C (II) and Zn (II) acetate are given in Table 2.
The assignment of the absorption bands of the furfuryldicarbamide molecule was carried out according to [7-10].
Comparison of the free molecule of furfuryldi-carbamide and its complexes with metal acetates shows, that in the transition to complexes an essential change is observed in the bands ofvalense vibrations of the ether bond -C-O-C- furan ring.
The high-frequency shift of the valence vibration of & (-C - O - C) :by 7-9 cm The sixth coordination site is filled with a water molecule-1 and the preferential valence vibration of the C = O bond by 3-4 cm-1 indicates a simultaneous participation in the coordination of the oxygen atom of the furan ring and two nitrogen atoms of substituted amine groups.
Analysis of the values of the frequency 3(C - C) acetate group shows that in the complexes each
group is coordinated monodentately with the participation of a ring oxygen atom in the hydrogen bond. The sixth coordination place is filled with a water molecule.
Derivatographic data of the thermolysis of furfu-ryldicarbamide of its complexes with cobalt, copper and zinc acetates are given in (Table 3).
The endothermic effects at 142, 220 and exothermic effects at 165, 200, 320, 490, 590, 650 °C appear on the heating curve of the derivatogram of furfuryl dicarbamide.
The first one corresponds to the melting of an organic ligand. The presence of subsequent thermal effects is due to the stepwise decomposition and combustion of the thermal decomposition products of substituted carbamide molecules.
Conclusion
The thermal behavior of coordination compounds depends on the nature of metals and is characterized by dehydration, deactivation, stepwise decomposition and burning of thermal decomposition products.
On the basis of elemental, X-ray phase, derivatographic analysis and spectroscopic data, the following possible structure should be proposed:
Table 2. - Some characteristic frequencies (cm-1) in IR absorption spectra of furfuryldicarbamide and its complexes with acetates of divalent cobalt, copper and zinc
Furfuryldicarbamide - L Co(CH3COO)2.L.3H2O Cu(CH3COO)2LH2O Zn(CH3COO)2L2H2O
fre-quen-cies absorption fre-quen-cies absorption fre-quen-cies absorption fre-quen-cies absorption
3449 ^as(NH2) 3536, 3424 9as(OH)HA 3570, 3470 9as(OH)HA 9as(NH2) 3530, 3460 9as(OH)HA 9as(NH2)
3348 5s(NH2) 3348, 3257 9s(OH)H2O, 25 (NH2) 3424, 3335 9s(OH)H2O, 25 (NH2) 2 3430, 3335 9s(OH)H2O, 25 (NH2), 9 (NH2)
3140 9 (CH)f.r. 3112 9 (CH)fr. 3110 9 (CH)fr. 3111 9 (CH)fr.
1666 9 (CO), 5 (NH2) 1670 9 (CO), 5 (NH2) 1669 9 (CO), 5 (NH2) 1670 9 (CO), 5 (NH2)
1631 9 (CO), 5 (NH2) 1628 5 (NH2), 5 (HOH) 1627 5 (HOH), 5 (NH2) 1629 5 (HOH), 5 (NH2)
1594 1574 5 , 9 (COC) K asv 1479 9 ,9 (COO) k asv 1601 9as(CO°)
1536 5 K 1603 9as(COO) 1557 9 K
1466 9 (CN) 1441, 1436 1417 9 (CN)+9 3(COO) 1436 1416 9 (CN) 1456 1417 9 (CN),9 s(COO)
1377 5 (CH) 1344 5 (CH) 1355 5 (CH) 1378 5 (CH)
1310 5 (CH)
1253 1229 9 (-C-O-C-) 1256 1236 9 (-C-O-C-) 1258 1236 9 (-C-O-C-) 1257 1238 9 (-C-C-C-)
1149 P (NH2) 1158 P (nh2) 1181 P (nh2) 1180 P (nh2)
1077 9 (CN)+ 1057 9 (CN), 1049 9 (CN)+ 1047 9 (CN)+
1010 + 9 (-C-O-C-) 1023 9 (-C-C-C-) 1032 + 9 (-C-O-C-) 1018 + 9 (-C-C-C-)
960 9 (CC) acet. 950 9 (CC)acet. 953 9 (CC) acet.
884 9 k (fur.r.) 895 9 k (fur.r.) 893 9 k (fur.r.) 895 9 k (fur.r.)
744 5 (NH2) 753 5 (NH2) 783 5 (NH2) 780 5 (NH2)
671 617 5 (COO) 685 5 (COO) 692 5 (COO)
559 5 (C) 527 5 (NCN) 629, 615 549 5 (NCN) 622 551 5 (NCN)
Table 3.- Derivatographic data of thermolysis of furfuryldicarbamide and its complexes with acetates divalent cobalt, copper and zinc
Compound Temperature effect interval, °C Peak effect, °C Loss of mass, Cu,% Total weight loss, Cu,% Nature effects The resulting compound
1 2 3 4 5 6 7
Furfuryldicarbamide (l) Removal of the hydrate molecule of water 130-143 142 0.05 0.05 endothermic furfuryldicarbamide
143-182 165 2.27 2.32 exothermic decomposition start
182-205 200 5.68 8.00 exothermic intensive decomposition
205-280 220 32.95 40.95 endothermic thermolysis
280-420 320 30.11 71.06 exothermic Thermolysis and combustion of thermolysis products
420-542 490 21.59 92.65 exothermic decomposition
542-595 590 6.80 99.45 exothermic decomposition
595-770 650 0.40 99.85 exothermic Burning thermolysis products
Co(CH3COO)2-•L.3H2O 60-105 90 3.52 3.52 endothermic Removal of the hydrate molecule of water
105-160 120 8.69 12.21 endothermic Removal of coordinated molecules
160-180 175 2.72 14.93 endothermic The decomposition of the anhydrous complex began
180-212 210 1.96 16.89 endothermic decomposition
212-258 245 2.72 19.61 endothermic decomposition
258-320 300 7.06 26.67 endothermic decomposition
320-380 350 17.39 44.06 exothermic decomposition with combustion of
Cu(CH3COO)2-.(L).0,5H2O 380-510 465 22.28 66.34 exothermic decomposition with combustion of thermolysis products
510-890 880 3.05 69.39 endothermic decomposition of cobalt carbonate
100-130 125 2.06 2.06 endothermic dehydration
130-155 150 2.50 4.56 endothermic dehydration complex
155-185 170 7.60 12.21 endothermic the beginning of decomposition of anhydrous complex
Zn(CH3COO)2-.(l).2h2o 185-235 230 34.78 46.99 endothermic intensive decomposition
235-275 278 13.04 60.03 exothermic decomposition
275-325 290 -0.30 59.73 exothermic oxidation of thermal decomposition products
325-380 345 -0.60 59.13 exothermic oxidation of thermolysis products
1 2 3 4 5 6 7
380-500 440 -0.50 58.63 exothermic oxidation of thermolysis products
100-140 130 9.00 9.00 endothermic of education Zn(CH3COO),-L
Zn(CH3COO)2-.(L).2H2O 140-182 150 11.58 20.58 endothermic the beginning of decomposition of anhydrous complex
182-250 210 19.28 39.85 endothermic intensive decomposition
250-320 258 24.68 60.54 endothermic thermolysis
320-410 380 6.02 66.56 exothermic thermolysis of a combustion product decomposed
410-480 430 2.89 69.45 exothermic Thermolysis and formation of zinc oxide
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