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    10 views18 pages

    09 - Chapter3 Ir Spectros

    Uploaded by

    Gabriela Ciubotaru
    ir spectrocopy

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    © All Rights Reserved
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    of 18
    CHAPTER-3 CHARACTERIZATION 40 {[Co(en)sJCl; have been able to stabilize some large anions but their potential as anion receptors has not been studied before. Therefore it was considered worthwhile to investigate the potential of cationic cobalt as anion receptors. The cationic cobalt complex fulfills the criterion of an anion receptor, i.e. unit positive charge for electrostatic interaction, eight N-H hydrogen bond donor groups and a stable framework. The potential of these cationic cobaltammines as anion receptors has been investigated here. In these, the cobalt(III) metal center is octahedrally coordinated by two ethylenediamine ligands and two monodentate ligands, but the complex cation has some differences in geometries and shapes, As a result, these are expected to show different anion receptor (complexing) properties with various anions. Describes the experimental methods and techniques adopted as such from the literature to prepare and purify the __— starting materials, unknown {tris(ethylenediamine)cobali(II1)] Chloride complex salts containing various anions has also been given. The identity of these compounds synthesized during the course of present investigations has been established with the help of elemental analysis and different spectroscopic techniques ('H and °C NMR, and vibrational spectroscopy). The physical and analytical data along with the percentage yield of the product obtained has also been incorporated. 1, Elemental analysis C, H, N was estimated microanalytically on an elemental analyzer PERKIN ELMER 2400 CHN elemental analyzer. Cobalt was estimated [1] gravimetrically as Co,03.Weighed out accurately about 0.8 g of the sample in about 50 ml HzO, added 3 ml 10% NaOH solution to decompose the complex 41 rapidly, warmed if necessary. Filtered through GF paper and washed the residue of Coz03 with hot water. Transfered the filter paper carefully and quantitatively to a conical flask acidify liberally with dilute HCI after adding 1.5 g KI. Covered with a watch glass and allow to stand until all the black Co,0; dissolved. Titrated the liberated iodine against standardised 0.05 M thiosulphate, adding 2 ml freshly prepared starch solution when the colour is straw yellow. Calculated the % Co in the sample and hence its % purity. We. of Co,05 3899 We. of compound taken 165.83 Percentage of cobalt = Chlorine was determined gravimetrically as AgCl. The aqueous solution of chloride salt was acidified with dilute nitric acid. A slight excess of AgNO; was added to it. Chloride was precipitated as silver chloride. Calculated the % chloride in the sample, Percentage of chlorine = _Wtof AgCl__ Wi of compound 2. Melting point All melting points are uncorrected and expressed in centigrade (°C), The melting points were determined by heating the Thiele’s tube filled with paraffin wax and taking the dried sample in a capillary tube. 3. Electronic Spectra UV spectra were recorded using HITACHI 330 spectrophotometer. 4, NMR spectra "H-NMR spectra were recorded using BRUKER AC 300 F(300MHz) spectrometer [2]. The chemical shift values are expressed as (6) value using deutrated dimethyl sulphoxide (DMSO) and CDCl; as an internal standard. 5. IR Spectra IR spectra of all samples were recorded using PERKIN ELMER spectrum RXFT-IR system. Samples were run as KBr Pellets and spectra recorded in the range of 4000-400cm"™ 6. Solubility product measurement Solubilty of the newly synthesized complex salts were measured at the temperature 25 + 2°C. This is done by dissolving a solute in a known amount of water until it becomes a saturated solution. Solubility product constants are used to describe saturated solutions of ionic comounds of relatively low solubility [3]. A saturated solution is in a state of dynamic equilibrium between the dissolved, dissociated, ionic compound and the undissolved solid, A:Bys)_ = ———+xA(aq) + yB™(aq) Equilibrium constant for such a process can be written as: Ky=[xa"} + [BYP Equilibrium constant is the product of concentration of the ions present in saturated solution of an ionic compound. Hence the name solubility product and is represented by symbol K.p. 7. Conductance measurement Conductances were measured with a calibrated digital conductivity meter; model PICO from LABINDIA, at a frequency of 1000 Hz. A range of concentation of the salts in each case was produced by adding stock solution of appropriate concentration from bureite to known quantity of the solvent taken in the beaker by dipping a conductivity cell. The solvent corrections ‘were applied in all the cases. All the measurements were carried in a water 43 thermostat bath maintained at 25.00 25:0.01°C. Before use, the conductivity cell was thoroughly cleaned with dilute nitric acid followed by washing with distilled water. Finally it was rinsed with anhydrous acetone and dried by blowing warm air [4]. The conductances of complex salts were measured at different concentraions and Molar conductance were cacluated by using the formula: Molar conductance = KxV Kx ¢ Where, K = Specific conductance (cell constant x conductane) C= molar concentarions ‘V=volume in ml. Results and discussion In the [Co(en);]Cls, cobalt(II) metal center is octahedrally coordinated by two ethylenediamine ligands and two monodentate ligands, but the complex cation hhas some differences in geometries and shapes. As a result, these are expected to show different anion receptor (complexing) properties with various anions. ‘Along with this, various diversifying reactions are possible with these cations as reported in literature. We have also explored some diversifying reactions of [Co(en)sJCl; under different reaction conditions which gave rise to interesting complex salts, When stoichiometric amount of [Tris(ethylenediamine)cobalt(IID} chloride complex salt and appropriate salts of different anions were separately dissolved in water and mixed with stirring, colored complex salts of the type [Co(en)sChaJR were R = MnO¥, SCN, (C204), Ass", [Fe(CN)]* were obtained in nearly quantitative yield in most of the cases. ‘Table 1.3: Reactants and Products Reactants Products [Co(en)s]Cls + KSCN [Co(en)s]SCNCh [Co(en):]Cls +KMn0s [Cofen)s] MnO.Clp [Coten)s]Cls +NaxC20« [Co(en)s]C20.C1 [Cofen)s]Cls + KsFe(CN)o [Co(en)s][Fe(CN)s] [Cofen)s]Cls + NasAsOs [Co(en)s]AsO« 45 ‘Table 1.4: Solubility of Co(II) Complexes S.N_ | Complexes Water |DMSO | Acetone | Methanol | Alcohol 1) | {ColenmsISCNC [Soluble | Soluble Tnsoluble | Insoluble | Insoluble Fy | [CateasIMinO,Ch | Soluble [Soluble | Insoluble ] Soluble Insoluble By] [eoten)s]G04Cl | Insoluble | Soluble "| Insoluble Tnsoluble | Insoluble 4 [(Cotens]Fe(CN]s | Soluble | Soluble Tnsoluble | Insoluble | Insoluble 5) _ | (Co(en)sJAsOx Toluble | Soluble | Insoluble | Soluble | Insoluble Solubility of ionic salts in water differs to a great extent and on the basis of solubility criterion; the salts are classified into three categories soluble, slightly soluble and sparingly soluble, The solubility measurements could provide an idea of the association between cations and anions. The higher value of solubility product shows lesser association while the lower value indicates higher association between cation and anion. Table 1.5: Color and melting point of Co(II1) Complexes. ‘Complexes Color Melting Point ec) [Co(en),JSENCh Light orange erystal 265 [Co(en)s] Mn0.Cle ‘Brownish powder 225-235 (D) [Co(en)3]C20Cl ‘Dark orange crystal 275 [Co(en)s][Fe(CN)s] Bright orange powder | 250-255 (D) [Co(en)s]AsOs ‘Bright orange crystal 275 ‘Table 1.6: Yield and percentage of Co(II) complexes ‘Complexes [Cofen)sJSCNCl2 [Co(en)s] MnOxCle [Co(en);}C20.Cl [Co(en)s]LFe(CN)<) [Co(en);]AsOx 47 IR spectra = IR spectroscopy is very instrumental in confirming the presence of cations in new salts, IR spectra of [Co(en)s]Cl; showed the characteristic bands corresponding to N-H, C-H and Co-N region. IR spectra showed characteristic absorption bands in the region 4000-400cm'' [5, 6]. An IR spectrum of the newly synthesized complex has been recorded in the region 4000-400cm" [7] and tentative assignments have been made on the basis of earlier reports in literature. IR bands at 1570, 1577 em’! are assigned to NH asymmetric deformation which indicates the trans- geometry of the complex. The IR band at 889 om" [8] is assigned to CH: rocking region. The IR band at 428 is assigned to Co-N. Table 1.7: IR spectral data of newly synthesized Co(II) complexes NO. | [Cofen}JSCNCI, | [Cofen),}MaO.CI, | [CofenJCLO.CI ] [CofenhIIFACND] | Cofen)s]As0. | assignment i 2927 2950 2952 2963 2965 | v(C-H) 2 | 1573,1578 | 1572,1577 | 1570,1579 | 1570,1576 | 1576,1578 | v.(NH:) 3 853 390 892 890) 392 | v(CH2) 4 420 453 460 459 455 | v(Co-N) NMR Spectra NMR spectroscopy furnishes an unambiguous method of assigning the configurations of the molecules [Co(en)s]Cls,[Co(en)s]SCNCh, _ [Co(en)]Mn0,Ch, [Co(en);]C,0.C1, [Co(en)s]EFe(CN)«], [Co(en)s]AsOs, The chemical shift values are expressed as 6 value (ppm) downfield from tetramethylsilane as internal standard. NMR of all these compounds was reported in DMSO-dg as solvent except [Co(en)s]SCNCI; of which is reported in DO. The protons of four NH groups in ethylenediamine group were observed in the range 4.8, 4.9, 5.1, 5.2 [9]. The CH: protons were observed at around 2.4 ppm. The C NMR spectrum shows the characteristic signal at 45 ppm for carbons of ethylenediamine group in both the title complex salts [10, 11]. Table 1.8: NMR spectral data of newly synthesized Co(II) complexes ‘Complexes "HNMR ®CNMR 4 (ppm) 8 (ppm) 5.3(6, 16H, NH-es) [Co(en)s]SCNCh, 20(6, 16H, CH, | 57 4C- CHa) [Co(en)s] MnO,Cl, 5.2(s, 16H, NH-n) | 44.7 (4C, CH-ex) 2.8(s, 16H, CH-ex) [Co(en)s]C20.C1 5.2(8, 16H, NH) 2,8(6, 16H, CH-ex) [Co(en)s][Fe(CN)s) 5.3(6, 16H, NH-.,) | 44.8 (4C, CH.) 2.8(6, 16H, CH-.0) [Co(en)s]AsOs 5.3(8, 16H, NH) | 44.8 (4C, CH) 2.8(6, 16H, CHa) * Molar Conductance [Co(en);][Fe(CN)6] ‘Conductance measurement studies in aqueous medium at 25°C were made and the plot A (molar conductance) versus concentration is presented. When the concentration was extrapolated to zero, the value of [Co(en)s][Fe(CN),] is measured to be 139.4 Sm’mol" which is within the range [12] reported as 1:1 electrolyte in aqueous medium. [ofen),IFe(ON}d Figure 16: Plot of square root of concentration versus molar conductance of [Co(en)s][Fe(CN)o] [Co(en)]AsOg When the concentration was extrapolated to zero, it gave the values of A, = 55.7 Sm*mol" for [Co(en);]AsOs which is within the range reported for a 1:1 electrolyte. Figure 17: Plot of square root of concentration versus molar conductance. [Co(en);] MnO,Cl, Conductance measurement studies in aqueous medium at 25°C were made and the plot A (molar conductance) versus concentration is presented as bellow. When the concentration was extrapolated to zero, it gave the values of Ay = 113.6 Sm’mol" for, {Co(en)s] MnO.Cl, which is within the range reported for a 1:2 electrolyte [13] [Co(en),]Mno,Cl, Figure 18: Plot of square root of concentration versus molar conductance. [Co(en);]SCNCI, ‘When the concentration was extrapolated to zero, it gave the values of Ao = 81.5 Sm*mo! for [Cofen)s]SCNCl,, which is within the Tange reported for a 1:1 electrolyte. [Cofen),]scNcI, Figure 19: Plot of square root of concentration Versus molar conductance, [Co(en)3]C,0,C1 Conductance measurement studies in aqueous medium at 25°C were made and the plot A (molar conductance) versus concentration is presented. When the Concentration was extrapolated to 7eT0, it gave the value A, = 264.1] Sm*mot"! which is within the range reported for a 1:2 electrolyte, [Cofen),1¢,0,c1 Figure 20: Plot of square root of concentration versus molar conductance Solubility products (K,,) and Electronic spectral maxima of newly synthesized complex anions. The electronic Spectra of the novel complex salts were recorded in H,0. These absorptions correspond to d-d transitions typical for octahedral low spin cobalt(III) [14]. These transitions are from ‘Aig ground state of cobalt(III) to singlet state 'T,, (Qow energy) and from "Aig ground state to ‘Tay (higher energy). UV/Visible spectra of complex salts ‘The electronic spectra of the newly synthesized complex salts have been recorded in Water. The solution state UV/visible absorption spectra of the complex salts showed absorption at around 600 nm in the form of a shoulder and strong absorptions at around 400 & 300 nm [15]. These absorptions correspond to d-d transitions typical 33 for octahedral Jow spin cobalt(III). The transitions are from 'Aig ground state of cobalt(III) to singlet state 'Ty, (low energy) and from "Aig ground state to ‘Tae (higher energy). Solubility product measurement Solubility of ionic salts in water differs to a great extent and on the basis of solubility criterion, the salts are classified into three categories (a) solubility > 0.1M (soluble), (b) solubility between 0.01M and 0.1M (slightly soluble) and (c) solubility < 0.01M (sparingly soluble). The solubility products of Co(en)sCls salts are 2.03 x 10°, 2.29 x 10°, 2.53 x 104, 6.89 x 10°, 3.48 x 10%, 1.00 x 10%, 1.98 x 10° which indicates that the affinity or binding of cationic cobaltammine is in the order MnO

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