Research Journal of Chemical Sciences ______________________________________________ ISSN 2231-606X Vol. 4(5), 41-47, May (2014) Res. J. Chem. Sci. International Science Congress Association 41 Synthesis and Characterization of some Cr+3, Fe+3, Co+2, Ni+2, Cu+2 and Zn+2Complexes with N-Phthalyl amino acid ligandsNagham S. Buttrus College of Dentistry, University of Mosul, Mosul, IRAQAvailable online at: www.isca.in, www.isca.me Received 8th January 2014, revised 25th February 2014, accepted 30th April 2014Abstract Two new sodium N-phthalyl amino acid ligands (L) and (L) were prepared by the reaction of phthalic anhydride with glycine or alanine amino acids the sodium salt of the above ligand were prepared by the reaction with sodium hydroxide. The mono and dinuclear complexes of Cr+3, Fe+3, Co+2, Ni+2, Cu+2 and Zn+2 were prepared by the reaction of the above ligands with the metal chloride in (1:1)or (1:2) metal to ligands ratio. The ligands and their complexes have been characterized by their analytical, spectral data, conductivity and magnetic measurements. Electronic spectra and magnetic measurements indicates that the mononuclear complexes contain tetrahedral environment, while the dinuclear complexes have octahedral geometry. Keywords: Synthesis, characterization, complexes, n-phthalyl amino acid, ligands. Introduction Interactions between transition metal and amino acids are very interesting in the biological applications. Complexes of some metals ions with amino acids can be used as models to study the pharmacodynamic effects of drugs or for increasing the biocompatibility and minimize toxic effects of some metal in Schroev and Abram U., Grecu I., Sandulescu R. and Neamtu M. and Grecu I., Neamtu M. and Enescn L.. There are many reports in the literature on mixed ligand complex of amino acids. Srivastava and Gupta et.al4-6 reported the synthesis and characterization of mixed ligand transition metal complexes formed with glycine, alanine, uracil, 2-thiouracil, thymine, adenine, histamine, valine and Lucien. A series of complexes of Cu(II) and Mn(II) with 4-(4'-halobenzene sulfonyl) benzoyl glycine and 4-(4'-halobenzenesolfonyl) – benzoyl – alanine with formula [M(L-H)(HO)] have been synthesized and characterized as mononuclear species on the basis of elemental chemical analysis, electronic and infrared spectra and molar conductivity measurements. The IR spectra indicated the presence of amino acid derivatives as coordinated through nitrogen atom and the oxygen from carboxylic group. The experimental data suggest that the ligands act as bidentate and adopt an octahedral stereochemistry. The coordination properties of the novel conjugate to wards copper ions were investigated. The performed studies exhibited the unusual binding properties of the ligand molecule having two potential strong coordination sites, namely dipeptide chain and pyridyl nitrogens. On the bases of potentiometric and spectroscopic studies the binding at the low pH values to the aromatic entity is suggested, while the rise of pH yielded the dimeric head to tail complex formation. The use of a ligand directed strategy in the assembly of discrete cluster, 2D layer and 3D networks, using N-substituted glycine derivatives with o-iodobenzoyl (a bulky substituted) or pyrimidyl, create a new possibility in the design of coordination networks . The synthesis and crystalline structure of the ligand N(pyrimidyl) glycine (1), its sliver derivatives [Ag (pyr-gly)] 0.5 HO (2) and the sliver derivatives of o-iodohippuric acid [Ag(I-hip)] 1.25 HO (3) are described by Oliver M.B. et al. In this paper we proposed to prepare a series of Cr+3, Fe+3, Co+2, Ni+2, Cu+2 and Zn+2 complexes with sodium phthalated amino acids derived from glycine and alanine. Material and Methods Experimental: All chemical were of reagent grade quality and were purchased from commercial sources (BDH and Fluka). They were used without further purification. Physical characterization: Elemental analysis of isolated complexes (C,H,N) were accomplished by the microanalytical laboratory at Dicle University Science and Technology Center (Du BTAM ) Turky. Metal content analyses were made on Shimadzu AA670 atomic absorption spectrophotometer. Infrared spectra were recorded using the Fourier-Transform Spectrophotometer Tesor 27Co Bruker in the range 4000-200 cm-1 with CsI pellets. The electronic spectra were recorded on a Shimadzu UV160 for the 10-3 M solution of complex in dimethyl- formamide (DMF) at 25°C. Conductivity measurements were carried out with 10-3 M solution of complexes in DMF at ambient temperature using a Jenway 4070 conductivity meter. The magnetic measurements were carried out on the solids by Faraday's method using Bruker BM6 instrument. Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 4(5), 41-47, May (2014) Res. J. Chem. Sci. International Science Congress Association 42 Synthesis of ligands: Ligands were prepared using the reaction between Phthalic anhydride with the recommended amino acid. (glycine or alanine)10. Properties of sodium salt of (L) and (L): The reaction of equimolar amount of phthalyl glycine (0.21g, 0.001 mol) or phthalyl alanine(0.22g, 0.001 mol) in 20 ml ethanol with NaOH (0.04g, 0.001 mol) in 20 ml ethanol. The mixture was boiled under reflux for 2 h. The product was obtained through evaporation of the solvent, then the precipitate was wash several times with ethanol and diethylether, then dried under vacuum for several hours. preparation the complexes [M(L)Cl] M=Co+2,Ni+2,Cu+2,Zn+2 : A solution CoCl .6HO (0.24g, 0.001 mol ) in ethanol 10 ml was added drop wise to a solution of sodium phthalyl glycine (0.23g,0.001 mol) or sodium phthalyl alanine (0.24g, 0.001) in 10 ml methanol. The mixture was refluxed for 2 h, then the solution was allowed to cool to room temperature. The solid thus formed was filtered off, washed with ethanol followed by diethylether and dried under vacuum for 4h.The other complexes were prepared similarly. Preparation of complexes [M(L)]Cl M=Fe+3 and Cr+3: A solution of CrCl. HO (0.27g , 0.001 mol ) in ethanol 10 ml was added for a solution of sodium phthalyl glycine (0.46 g, 0.002 mol) of sodium phthalyl alanine (0.48g , 0.002 m0l) in 10 ml ethanol, the mixture was refluxed for 3h , the solution was cooled to room temperature .The isolated solid was filtered off, washed several times with ethanol in order to remove the formed NaCl salt, then diethylether and dried under vacuum for several hours. Results and Discussion Sodium phthalyl glycine (L) and sodium phthalyl alanine (L) were prepared the by reaction of phthalic anhydride with glycine or alanine (amino acid) heated in a sand bath (scheme 1) and then treated with a sodium hydroxide. Scheme-1 Preparation of the ligands Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 4(5), 41-47, May (2014) Res. J. Chem. Sci. International Science Congress Association 43 The complexes were prepared through direct substitution of chloride by the relevant phthalyl ligands as oxygen donors for the metal ions. All complexes are thermally stable and insoluble in organic solvent, however fair solubility was attributed in DMSO (dimethyl solfoxide) and DMF (dimethylformamide). The 10-3M solution for, Co+2, Ni+2, Cu+2 and Zn+2 complexes display molar conductance equal to 20-50 ohm-1.cm.mol-1 (table 1) indicating neutral nature of the complexes, while the, Cr+2 and Fe+2 complexes have molar conductance of 130-172 ohm.cm.mol-1 indicating a 1:2 electrolytic nature11, this is consistent with stoichiometry for the complexes on the basis of analytical data. The most important diagnostic feature of IR spectra of the complexes were listed in table 2. The most significant information on the geometry of these complexes were came from the analysis carboxylate and carbonyl absorption region. Stretching frequencies of these functional groups are closely related to the way in which they are coordinated to the metal ions12. The ligands band due to carboxylate group may be coordinated to the metal ions either in monodentate or in bidentate manner. The FTIR consistent with the formation of well defined compound with the above composition. The carboxylate group is able to coordinate to metal ions in different mode13. When the carboxylate group coordinate to metal ion in mono- deutate manner, the difference between the wave number of a symmetric and symmetric stretching band (= asymCOO-symCOO) is larger than observed for ionic compounds, when the ligand chelate is bidentate  considerably smaller than that for acetate group in ionic compounds. Two bands are observed at 1626-1587 and 1414-1427 cm-1 and the difference in COO 141-194 cm-1 table 2 are indicative of bidentate nature of the carboxylate groups14. However, the bands observed at 1697-1722 cm-1 for the complexes may be assigned to the free carbonyl groups, and the other carbonyl groups are shared in coordination Further support for this argument came from IR of the complexes which showed new bands at 530-577 cm-1 and also a band at 290-330cm-1 which may attributable to (M-O) and (M-Cl) respectively15. The IR spectra of Ni(II) and Fe(II) complexes are shown in figure 2. The electronic spectra of the ligands and their complexes are summarized in table 2. The results obtained are in good agreement with other spectra and the literature16. The bands observed at 34246 and 33113 cm-1 are due to the n- or * transitions with in the ligands. The magnetic moment values of chromium complexes (1,7) are 3.75-3.89 B.M suggest the presence of three unpaired electro, which reveal the spin free nature of the complexes corresponding an octahedral geometry17. The electronic spectra of Cr(III) complexes show two bands at 17241,17301 and 23584 and 23696 cm-1 which may be assigned to g(F), 4g(F)( ) and g(F) g(F)( ) in octahedral geometry. The magnetic moments of octahedral high spin iron(III) complexes are normally very close to the spin only value of 5.92B.M 18. The electronic spectra of the prepared iron (III) complexes (table 2), the complexes exhibited absorption bands in the region (10224 and 10309) cm-1 referred for g Eg transition the absorption position for iron (III) complexes are consistent with be six coordinate octahedral iron (III) complexes. The magnetic moment values of Co(II) complexes (3 and 9) are (4.00-4.53)B.M These values correspond to get tetrahedral configuration, the Co(II) complexes gave more intense bands in the d-d electronic spectra at14880 and 15974 cm-1 which may be assigned to (F) (p) transition indicating tetrahedral geometry19. The magnetic moment values of Ni(II) complexes are 3.36 and 3.01 B.M at 25°C, suggest the presence of two unpaired electrons, which reveals the spin free nature of the complexes corresponding a tetrahedral stereochemistry. The nickel complexes show a bands at15060 and 14925 cm-1 due to (F) (p)( ) transition indicated for tetrahedral geometry20 and as showing in figure 2. The magnetic moments for copper (II) complexes vary in the range 1.81-1.89 B.M. This indicates that the complexes are monomeric in nature and in agreement with distorted tetrahedral geometry. The copper (II) complexes show a bands at14204 and 14044 cm-1 which correspond to the transition of the g g consistent with distorted tetrahedral geometry21. The Zn(II) complexes are diamagnetic and do not show any d-d transition bands indicating a tetrahedral geometry.Conclusion The results of this study indicated that the ligand is coordinated to the metal ions as monobasic tridentate from carboxylate and carbonyl groups in mononuclear and binuclear complexes. The magnetic moment and electronic spectral a studies suggest a tetrahedral and octahedral environment for the metal complexes at show in figure 1. Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 4(5), 41-47, May (2014) Res. J. Chem. Sci. International Science Congress Association 44 Figure-1 Suggested structures for the complexes Figure-2 The electronic spectrum of [Ni(L)Cl] complex Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 4(5), 41-47, May (2014) Res. J. Chem. Sci. International Science Congress Association 45 Wave numbers/ (cm-1) Figure-3 The IR spectrum of [Fe(L)Cl]Wave numbers/ (cm-1) Figure-4 The IR spectrum of [Ni(L)Cl] Transmittance/(%T) Transmittance/(%T) Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 4(5), 41-47, May (2014) Res. J. Chem. Sci. International Science Congress Association 46 Table-1 Physical properties and elemental analysis of the ligands and their complexes Seq. compound Color m.p (ºc) Yield % Analysis ,found (calc.)% () cm.ohm. mol-1eff C H N M 10NNa Yellowish 193-196 82 52.79(52.86) 2.58(2.64) 6.18(6.16) ---- --- --- 1 [Cr(L 1 ) 2 ]Cl 2 Olive 250d 75 45.00(45.19) 2.15(2.25) 5.20(5.27) 9.92(9.79) 170 3.75 2 [Fe(L 1 ) 2 ]Cl 2 Orange 160d 70 44.82(44.87) 2.29(2.24) 5.21(5.24) 10.03(10.44) 130 5.40 3 [Co(L 1 )Cl] Pink 260d 72 40.16(40.21) 1.99(2.01) 4.61(4.69) 19.69(19.74) 40 4.00 4 [Ni(L)Cl] Green 220-222 80 40.15(40.21) 1.98(2.01) 4.59(4.69) 19.58(19.68) 46 3.01 5 [Cu(L 1 )Cl] Blue 230d 78 40.00(39.60) 1.83(1.98) 4.58(4.62) 20.88(20.95) 30 1.81 6 [Zn(L 1 )Cl] White 240d 74 39.41(39.35) 1.85(1.96) 4.50(4.59) 21.22(21.45) 45 Dia 11NNa White 149-151 85 56.75(56.89) 4.00(3.88) 6.00(6.63) --- --- --- 7 [Cr(L 2 ) 2 ]Cl 2 Olive 230d 70 47.00(47.06) 3.19(3.21) 4.72(4.99) 9.25(9.21) 172 3.89 8 [Fe(L]Cl Orange 190-192 80 46.62(46.74) 3.11(3.18) 4.89(4.95) 9.95(9.89) 155 5.31 9 [Co(L)Cl] Violet 116-118 75 42.30(42.11) 2.81(2.87) 4.45(4.47) 18.71(18.79) 20 4.53 10 [Ni(L 2 )Cl] Green 192 d 72 42.10(42.15) 2.89(2.96) 4.41(4.47) 18.71(18.74) 40 3.36 11 [Cu(L)Cl] Blue 150-152 79 41.60(41.51) 2.90(2.83) 4.35(4.40) 19.86(19.96) 50 1.89 12 [Zn(L)Cl] White 181-183 81 41.11(41.26) 2.79(2.81) 4.31(4.37) 20.50(20.44) 40 Dia d= decomposition temperature. Table-2 Electronic and infrared spectral bands of the ligands and their complexes Complex no. Band maxima max) nm IR spectral bands (cm-1) as(COO) (COO) as- s ) (CO) (M-O) (M-Cl) 34246 1593 S 1473--- 1649 S --- --- 1 17241,23584 1604 S 1415 m189 1712 S 530 w --- 2 10224 1612 S 1415 m197 1720 S 469 w 330 w 3 14880 1597 S 1425 m172 1697 S 532 w 310 w 4 15060 1620 S 1422 m198 1701 S 532 w 300 5 14204 1597 S 1421 m 176 1716 S 530 w 300 w 6 34013 33112 1599 1480--- 1630 S --- --- 7 17301,23696 1562 S 1414 m148 1720 S 530 w 290 w 8 10309 1600 S 1417 m 183 1722 S 577 w 300 w 9 15974 1593 S 1420 m 173 1700 S 535 w 310 w 10 14925 1626 S1485 m 141 1722 S 553 w 300 w 11 14044 1631 S1477 m 154 1697 S 532 w 310 w 12 35211 1626 S1483 m 143 1722 S 553 w 290 w S= strong, m=medium, w= weak. Research Journal of Chemical Sciences ___________________________________________________________ ISSN 2231-606XVol. 4(5), 41-47, May (2014) Res. J. Chem. Sci. 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