IBN AL- HAITHAM J. FOR PURE & APPL. SCI. VOL.24 (2) 2011 Synthesis, Spectroscopic and Biological Studies of Some Metal Complexes with 2,3,5,6- O,O,O,O-tetraacetic acid L- ascorbic acid J. S. Sultan, A. A. Mukhlus, F. H. Musa Department of Chemistry, College of Education, Ibn Al- Haitham ,University of Baghdad Received in : 11 August 2010 Accepted in : 8 February 2011 Abstract The reaction of L-ascorbic acid with the chloroacetic acid in presence of potassium hydroxide has been investigated. The new product L (2,3,5,6-O,O,O,O-tetraacetic acid L-ascorbic acid) was isolated and characterized by elemental analysis(C.H), 1 H, 13 C-NM R. Mass spectrum and Fourier transform infrared (FT-IR). The reaction of the ligand (L) (where L = H4L), M +2 = (Co, Ni, Cu, Cd, Pb, Hg, Ca, Mg) has been investigated and was isolated and characterized by FT-IR, UV- visible, conductivity, Atomic absorption and molar ratio (Cd, Co) complexes. Spectroscopic evidence showed that the binding of the M(II) ions are throughy the O-1 Lacton, O-2-OCH2COOH and O-6-OCH2COOH resulting in a six- coordinated metal ion, , Kf, max, for Co, Cd complexes, were estimated,  for Co, Ni, complexes were calculated too. The study of biological activity of the ligand (L) and its complexes (Cu +2 , Cd +2 , Ca +2 ) showed various activity toward staphylococcus aureu and Escherichia coli, except Ca- complex didn't show any effect. Key word : Synthesis, Spectroscopic , Biological Studies Introduction Ascorbic acid has been reported to act in a number of ways. It acts as a biological hydrogen carier for redox enzyme systems in cell metabolism[1], as a food preservative by oxidative rancidity of fatty oily foods or to prevent discoloration of preserved fruits and vegetables[2,3]. Although ascorbic acid has a wide range of antimicrobial effects, some of its, oxidative products are toxic[4]. L-ascorbic acid molecule has four hydroxyl groups and all these groups are active for classical esterification[5,6] and formation Schiff base with amines complexes[7]. Some metal ions have been prepared and characterized[8]. In view of this, we have synthesized, and characterized, new ligand (L) and its complexes with M II ions where MII = (Co+2, Ni+2, Cu+2, Cd+2, Pb+2, Hg+2, Ca+ and Mg+2) with biological studies of ligand and its complexes (Cu+2, Cd +2 , Ca +2 ). Experimental Materials All chemicals were purchased from BDH, and used without further purifications. IBN AL- HAITHAM J. FOR PURE & APPL. SCI. VOL.24 (2) 2011 Instrumentation 1. Infra-red spectra between (400-4000 cm–1) 8300 (FT-IR) Shimadzu Spectrophotometer. 2. The electronic spectra were recorded on the UV-Visible spectrophotometer type (spectra 190-900) nm CECIL, England, using water as a solvent. 3. The melting point was recorded on "Gallen kamp Melting point Apparatus". 4. The Conductance Measurements were recorded on W. T. W. conductivity Meter. 5 The characterize of new ligand L is acheaved by: A: Elemental analysis for carbon, hydrogen was using a Euro Vector EA 3000 A Elemental Analysis (Italy). B: 1 H- and 13 C NM R spectra were recorded by using a bruker 300 MHZ (5witzerland). Chemical Shift of all 1 H- and 13 C-NM R spectra were recorded in  (ppm) unit downfield from internal reference tetramethylsilane (TMS), using D2O solvent. C: GCM S spectrum was performed GCM S solution/ Msc/ Msc-DI- unk, 9gm, company a Shimadzu model carried out QP 505 A, orgin: Japan. D: All these analysis were done in at AL-al-Bayt University , Al- Mafrag, Jordan. 6. Thin layer chromatography (TLC): The (TLC) was performed on aluminum plates coated with (0.25 mm) layer of silica gel F254 (Fluka), and were detected by iodine. Synthesis 1. Synthesis of 2,3,5,6-O,O,O,O-tetraacetic acid L-ascorbic acid To a solution of 0.176 gm (0.001 mole) of L-ascorbic acid in 20 ml aqueous ethanol (15 ml ethanol + 5ml water) were added a solution of 0.224 gm (0.004 mole) of potassium hydroxide in 5 ml of ethanol, after which the mixture was stirred for 30 minutes. To this mixture was added solution of 0.380 gm (0.004 mole) of chloroacetic acid in 10 ml of ethanol. Then the solution was stirring for one hour. The solution was evaporated slowly to bring down the orange precipitate. The product was recrystallized from (ethanol + water) in the ratio (15:5). The analytical results showed the composition (L) of C14H16O14.3H2O. EtOH.4KCl. Rf (0.526) in ethanol benzene (9:1). 2. Synthesis of 3,5-O,O,-diacetic acid-2,6- O,O diacetato L- ascorbic acid aqua metal (II), (M II =Co, Ni, Cu, Cd, Pb, Hg, Ca and Mg) All complexes were prepared as follows: To a solution of (1 m mole) of L in 20 ml ethanol was added a solution of (4 m mole) of potassium hydroxide in 5ml of ethanol. The mixture was stirred at room temperature for half hour. To this mixture was added solution of (1 m mole) of metal chloride in 20 ml of ethanol. Then the solution was stirring for one hour. The solution was evaporated slowly to bring down the complex. The complex was recrystallized from ethanol. The physical properties for all synthesized ligand L and its complexes are shown in Table (1-1) Results and Discussion 1. Synthesis of 2,3,5,6-O,O,O,O-tetea acetic acid L-ascorbic acid (L) In the present work of the ligand (L) was synthesized by reacting L-ascorbic acid with chloroacetic acid in presence of potassium hydroxide. 1 2 .3H2O. EtOH.4KCl 1 2 O O HO HO OHHO O CH2O CH2O OO 4ClCH2COOH HOOC HOOC H2C COOH CH2 COOH O 4KOH IBN AL- HAITHAM J. FOR PURE & APPL. SCI. VOL.24 (2) 2011 The infrared spectrum of the (L) lacked absorptions caused by (HO–CH2) which appeared in the spectrum of L-ascorbic acid at 3525, 3410, 3313 and 3213 cm –1 Fig. (1) respectively[9]. This confirms the disp lacement of the O–H hydrogen by mean of acetic group O–CH2COOH Fig. (2) (L). In the same trend broad band centered at 3421 cm –1 and bands in the range 2700-2500 cm –1, are related to carboxylic OH stretching. The band at 2954 cm–1 stretching is attributed to C–H aliphatic. The strong band at 1608, 1404, 941 and 570 cm–1 are attributed to the O=C–O stretching vibration[10,11]. The carbonyl (lactone C–I=O) stretching vibration appeared as band medium intensity at 1755 cm–1. Another medium broad band observed at ca. 1380cm –1 is assigned to C(3)–O – and the peak at 1319cm –1, (O(2)–H) for free acid shifted from the spectrum of L at 1311cm–1 which strongly indicates the binding of OCH2COOH with C–2 and C–3 in a new ligand (L)[12], Fig. (2). The mass spectrum of the ligand (L) Fig. (3a) showed a highest Mass m/e at 167 with signal intensity (3%), (relative to the base peak at m /e (44)) which may due to C8H7O4. The detailed decomposition path ways are summarized in the reaction scheme; Scheme (1): The fragmentation sequence of the ligand (L) with relative abundance NMR spectrum for the ligand (L) 1H–NMR. spectrum of the L in D2O exhibited (d) at  4.2 ppm for (IH) Lactone ring and O–CH2– at 4.8 ppm. Carboxylic acids usually absorbs in the region (8–9.5) ppm and this is out of scale. Evidence for the carboxylic of L has been observed from the 13C-NM R. spectra. The spectrum of L measured in D2O showed resonances typical for C=O at 177 and peak at 43 ppm is due to O–CH2 [8,9], as in Table (1–2), (1–3), Figs. (5a), (5b). C H HCH2O C HOOC CH2OHOOC H O O OO H CH2 COOH CH2 COOH O O O H 97 C4HO3 (8%) O O O H 111 C5H3O3 (6%) CH2 O O O H 125 C6H5O3 (4%) HH CH2 O O H 167 C8H7O4 (3%) HH CH2 57 27% CO2 44 (90%) OO HC CH 408 HC2O2 -C 6 H 9 O 10 -C2 H2 O -CH 2 -CH2 -C 2 O -C H IBN AL- HAITHAM J. FOR PURE & APPL. SCI. VOL.24 (2) 2011 The prepared complexes Reaction of the ligand (L) with metal salts MXn.YH2O, {where Y = H2O}, (X=Cl, NO3 with lead only), were carried out in ethanol- water under stirring in presence of potassium hydroxide. All complexes are stable, the analytical and physical data, in Table (1–1) and spectral data, in Table (1–4). All complexes are dissolving in water, DM SO and DMF solvents. IR spectra The comparative IR spectral study of the ligand L Fig. (2), and its complexes Fig. (3) (Co– complex as example). reveals the interesting coordination of the ligand during complex formation. The important IR bands with their possible assignment are depicted in Table (1–4). In general upon metal ion interaction, the presence broad band is observed at  3400 cm –1, weaks bands in the range 2700–2500 cm –1 and band at 1605 cm –1 are related to H–bonded– OH of acetic acid and carboxylic[23]. The carbonyl (C–I=O) stretching vibration is shifted towards a lower frequency at (1740–1730) cm –1 due to coordinate metal ion with lacton (C– I=O) and this band is assigned to (O–C=O) of lacton ring strongly suggest that the ligand acid ring is not ruptured in the course of the complexation. For instance the I.R. spectrum of [pt(dppm)Asc–O 2,O3] diphosphine (PP) the position of the (C=O) band of ascorbic acid at 1745 cm–1 shifts to lower frequency by between 30 and 50 cm –1 upon coordination to platinum[14]. This value compare favourably with that found for L–complexes. All complexes exhibits a broad absorption bands at 1593–1635 cm –1 due to the stretching vibration of C=C and (COO–). The appearance of new two bands in the 1495–1530 cm–1 range due to as(COO – ) and another one in the 1408–1427 cm –1 range assigned to s(COO – ). Accordingly, The antisymmetric and symmetric stretching vibration modes as(COO – ) and s(COO – ) of the group should help in elucidating the structure of our complexes[15]. The direction of the frequency shift of the as(COO–) and the s(COO–) bands with respect to those of the free ion depends on the coordination mode of the COO– group with the metal ion. Nakamoto and Mc carthy[16,17] claimed that if the coordination is monodentate the as(COO – ) and s(COO – ) will be shifted to higher and lower frequencies respectively. Whereas, if the coordination is chelating bidentate or bridging bidentate both as(COO–) and s(COO–) frequencies will change in the same direction. This is because the bond orders of both C=O bonds would change by the same amount. Based on these facts and comparing the as(COO–) and s(COO–) frequencies of the L complexes by the as(COO–) and s(COO–) frequencies of RuH(ac)(PPh3)2 (1582, 1449)[18], as shown in Table (1–4) and Fig. (3). One can say that all the prepared complexes are metal chelates, because both as(COO–) and s(COO–) frequencies changed in the same direction and the – values [as(COO–)–s(COO–)  (87–111) cm–1 which are significantly less than ionic values indicates that L–complexes contains carboxylic and bidentate carboxylato group in a molecule. The two carboxylic group in 2, 6 are bidentate coordinate and at in 3, 5 are carboxylic acid. Several other sharp absorption bands at 941 and 570 cm–1 of the free acid, which attributed to the COO– stretching vibration exhibited considerable shift and sp litting upon metal ion interaction. The band characteristic of coordinated water are seen in all complexes in the range (825–763) cm– 1 . The sharp absorption bands observed around 400 cm –1 [23], have been assigned to M–O stretch vibrational bands. These assignments are based on the fact that the M–O stretch bands for the most metal complexes occur within this region[15,16]. Electronic Spectra The electronic spectral data of free ligand and its complexes are summarized in Table (1–5). The peak at 246 nm (40650 cm –1 ) in the electronic spectrum of free lignad L Fig. (6) was shifted to lower frequency with tail start at 300–400 nm indicated to charge transfer were noticed in the electronic spectra of Pb, Hg, Cd, Mg and Ca[19]. IBN AL- HAITHAM J. FOR PURE & APPL. SCI. VOL.24 (2) 2011 LCu; six coordinate complexes, the ground state in an octahedral field is 2 Eg, it is subject to considerable Jahn– Teller distortion and in practice, the majority of copper (II) complexes which are usually green or blue are tetrgonally distorted. Such complexes give rise to one absorption band in the visible region near 13000 cm –1[11,27]. the spectrum of the green LCu complex is shown only a brood absorption band centered at 800 nm (12500 cm–1) due to the transition 2 Eg  2 T2g. LCo complex The most octahedral Co(II) complexes[28-30] are pink or reddish while the most tetrahedral Co(II) complexes are blue or green. These colour may indicate to stereochemistry. The LCo complex gives reddish colour and its UV–visible spectrum Fig. (7) is shown bands within range octahedral stereochemistry[8,9,11,17] and as follows; 2 = 680 nm (14706 cm–1) 4T1g  4A2g 3 = 590 nm (16949 cm–1) 4T1g  4T1g(p) The absorp tion within range 440 nm (22220 cm–1) which is assigned to charge transfer T2g  *. The transition 1, Dq, B and  are calculated theoretical limits, from the graphs Fig. a and Fig. b. 2 = 18 Dq 1-cm817 18 14706 Dq  1470 = 18 Dq 1 = 8 Dq = 8  817 = 6536 cm–1 3= 6Dq + 15 B – 16949 = 6  817 + 15 B– = 4902 + 15 B – 15 B – = 16949 – 4902 15 B – = 12047 803 15 12047 B cmoplex -  0.827 971 803 ionfree B complex B β -  IBN AL- HAITHAM J. FOR PURE & APPL. SCI. VOL.24 (2) 2011 Fig. (a) Energy level diagram (Tanabe- Sugano) for d 7 ions in an octahedral field (C=4.633B) Fig. (b) A2 and T1 ground states, transition energy ratios versus E(v3)/B (range 16-47). Note that the left-hand ordinate refers to E(v3)/B (16-24.6) and the right-hand ordinate to E(v3)/B (24.6-47) Co and Ni complexes LNi complex Six coordinate complex nickel (II) complexes exhibit a simple spectrum involving three sp in allowed transitions to the 3 T2g, 3 T1g(F) and 3 T1g(P) levels[8,9,11,17]. These occur in range 7000– 13.000, 11.000–20000 and 19000–27000 cm –1 regions respectively. In addition, two sp in forbidden bands to 1Eg and to 1T2g are frequently observed. When Dq/ B is nearly unity the 2 transition 3T1g(F) appears as a well defined doublet- this may be consequence of the transition to the 1Eg level gaining intensity through configurational interaction with the 3T1g(F)[24,25] although other authors prefer to interpret the structure in terms of sp in– orbital coupling[26]. From the above the L1Ni complex appears as a well defined doublt due to 3 A2g 3 T1g(F) 2776 nm (12987 cm –1 ) and 660 nm (15151 cm –1 ) due to 3 A2g  1 Eg. The third sp in allowed transitions to the 3T1g(p) 3 at 22000 cm–1 from the graph Fig. b. B, , 10q may be calculated in the following ways; 1.69 12987 22000 υ υ from 2 3  28B / )E(υand0.89 B Δq hence 3  B = 785.7 cm –1 10q = 6990 cm–1 = 1( 3T2g 3A2g) 0.76 1030 785.7 β  B for free ion Ni = 1030 IBN AL- HAITHAM J. FOR PURE & APPL. SCI. VOL.24 (2) 2011 Solutions chemistry Molar ratio The complexes of the ligand (L) with selected ions (Co+2, Cd+2) were studied in solution using water as solvents, in order to determine (M:L) ratio in the prepared complexes, following molar ratio method[21]. A series of solutions were prepared having a constant concentration (C) 10 –3 M of the hydrated metal salts and the ligand (L). The (M:L) ratio was determined from the relationship between the absorption of the observed light and mole ratio (M:L) found to be (1:1). The result of complexes formation in solution are shown in Table (6), Table (7) and Table (8), Fig. (8) and Fig. (9). Molar conductivity for the complexes of ligand (L) The molar conductance of the complexes in (water), Table (9) lie in the (90– 177.6) S.cm 2 molar –1 range, indicating their electrolytic nature with (1:1) ratio, except for the complexes, Ni, Cd, Pb, and Mg which their molar conductance lie in the (6.6– 42) Scm 2 Molar –1 range, indicating their non– electrolyte nature[20]. Biologcal effect of new ligand L and its complexes Indicating that the new ligand and its complexes exhibited antibacterial activity against both gram positive and gram negative bacteria[31-34], except Ca–complex has no effect on both bacteria. Table (10), Fig. (10) and Fig. (11). Conclusion A series of complexes of Co+2, Ni+2, Cu+2, Cd+2, Pb+2, Hg+2, Ca+2, Mg+2 with 2,3,5,6– O,O,O,O–tetraacetic acid L–ascorbic have been prepared and characterized. The ligand (L); two bidentate acetate 2,6 and O–1 Lacton are binding to metal ions and one molecule water forming octahedral structure leaving two groups of acetic are uncoordinated as follow: References 1. Gilula, N. B.; Epstein, M.L. and Beers, W.H. (1978), Cell– to–Cell–Communication and ovulation. A. Study of the cumulus– oocyte Complex–J–ce Biol. 78 (1): 58 – 75. 2. Pauling, L. (1972) "Vitamin C the Common cold and the Flu", Ed., W. H. Free man and company, San Francisco, PP. 33– 46 . 3. Lewin, S. (1976), "Vitamin C Its molecular Biology and Medical Potential". Ed. A cademic press, London, New York, San Francisco, PP. 11– 14. 4. Halli, B. (1996), Vitamine C: antioxidant or pro – oxidant in vitro; Free Rad. Res 25: 439– 454. 5. Masuo, M. and Hidenori, I. (1970), Yamanouchi pharmacentical Co., Ltd., Japan.8031, 661 (C1. C07d, A61K, A23L). IBN AL- HAITHAM J. FOR PURE & APPL. SCI. VOL.24 (2) 2011 6. Fodor, C. ;Arnold, R. and Mohacsi, T. (1983), A new role for L-ascorbic acid Michael donor to alpha, beta-unsaturated carbonyl compounds. Tetrahedron 39:2137-2145 . 7. Magdi, F. ;Iskander Mohamed, A.E.; Shaban, Susan M. El-Badry (2003), Carbohydrate Research, Sugar hydrazone- metal complexes , 338:2341-2347. 8. Tajmir- Riahi (1990), Coordination Chemistry of vitamin C. part I. Interaction of L- Ascorbic Acid with Alkaline Earth Metal Ions in the Crystalline Solid and Aqueous Solution, J. Inorg. Biochem; 40:181-188. 9. Tajmir- Riahi (1991), Coordination Chemistry of vitamin C. part (II). Interaction of L- Ascorbic Acid with Zn(II), Cd(II), Hg(II), and Mn(II) Ions in the solid state and in Aqueous solution, Int. J. Inorg. Biochem; 42:47-55. 10. John, R. Dyer, (1965), Applications of absorption spectroscopy of organic compounds, Englewood by prentic– Hali, Inc. 11. Kazvo Nakamoto (1986), John Wiley & Sons, Inc., Infrared and Raman Spectra of Inorganic and Coordination Compounds Fourth edition. 12. Birgül Zümreogh– Karan, Ahmet N– Ay and Canan Ünaleroglu, (2005), (structural and magnetic studies on mono-and polynuclear chromium ascorbate complexes. Transition Metal Chemistry, 30:451– 459. 13. Parikh, V. M. (1985),"Absorption Spectroscopy of organic Molecules". 14. Malcolm, J.; Arendse, Gordonk- Anderson and Nigam, P. Rath,(1999), Synthesis and characterization of Platinum (II) Complexes of L- Ascorbic Acid, Inorg. Chem., 38:5864-5869. 15. Mesubi, M. A. (1982), "An infrared study of Zinc, Cadmium and lead salts of some fatty acids", Journal of Moleculular structure, Vol. 81:No. 1–2, PP. 61– 71. 16. Washed, M. G. A.; Refat, M. S. and El Megharbel, S. M. (2009), "Synthesis spectroscopic and thermal characterization of some transition metal complexes of folic acid", Spectrochimia Acta A, Vol. 70(4): 916– 922 . 17. Nakamato, K. and Mccarthy , P. J. (1968), John Wiley & sons. New York, NY, USA, Spectroscopy and Structure of Metal Chelate Compounds. 18. John, R. Dyer, (1965), Inc Application of absorption spectroscopy of organic compound, prentic- Hall, 19. Williamkemp (1987), "Organic spectroscopy" 2nd, Edition. 20. Kettle, S. F. (1975), "Coordination compounds", Thomas Nelson and sons, London, P. 165. 21. Skoog D.A., Donald M. west (1974), Fundamentals of Analytical Chemistry Altoit London Edition. IBN AL- HAITHAM J. FOR PURE & APPL. SCI. VOL.24 (2) 2011 22. Farrington Daniels and Robert Alberty, A. (1975), "Physical Chemistry" 4th, ed. 23. Clegg, D. E. and Hall ,R. J. (1969), Decomposition of Ascorbic Acid in the presence of cadmium ions leads to formation of a polymeric cadmium oxalate species with peruliar structural features, J. Organ metal chem., 17: 175. 24. Holmes, O. G. and Mc Clure, D. S. (1957), Synthesis and Characterization of some metal complexes of Vitamic c. Part 1,2 –Ascorbate Complexes of Mn(II), Fe(III) and Co(II), J. chem. Phys., 26. 25. Sutton, D. (1968), Electronic spectra of Transition Metal Complexes Mc GRAW-HILL., London. 26. Geary, W.J. (1970), "Coorination Chemistry Reviews" Elsevier publishing company Amsterdam. 27. Lever, A. B. P. (1968), Elsevier publisihing company "In organic electronic spectroscopy". 28. Rakesh, K. ;Sharma, Munirathnam Nethaji and Ashoka, G. Sumuleson, (2008), Asymmetric allylic alkylation by palladium – bisphosphinites, Tetrahedron; Asymmetry , 19: 555–663. 29. Khen, F. and khanam, A. (2008), Study of Complexes of cadmium with some L- amino acids and Vitamin-C by Voltammetric technique, Ecl. Quim, Saopaulo, 33, numero 2:29–36. 30. Tahereh Rohani, Mohammed Ali Taher (2009), Talanta, Anew method for electrocatalytic oxidation of ascorbic acid at the Cu(II) Zeolite-Modified electrode, 78: 743 – 747. 31. Anacona, J. R. (2001), Syathesis and antibacterial activity of some metal complexes of - Lactams antibiotics, J. coord. Chem., 54: 355–365. 32. Petra, D. ;Tetjana, Z. and Boris, P. et al., (2005), "Mixed- valence Cu(II)/ Cu(I) complex of quinolone ciprofloxacin isolated by ahydrothermal reaction in the presence of L– histidine comparison a biological activities of various copper- ciprofloxacin compounds", Journal of inorganic biochemistry, 99(2): 432– 442. 33. Tauber, S. C. and Nau,R. (2008), "Immunomodulatory properties of antibiotics", Current molecular pharmacology, Vol. 1, PP. 68–79. 34. Sultana, N. and Arayne, M. S. (2007), "In vitro activity of cefadroxil, cephalexin. Cefatrizine and cefpirome in presence of essential and trace elements", Pakistan Tournal of pharmaceutical sciences, 20(4): 305–310. IBN AL- HAITHAM J. FOR PURE & APPL. SCI. VOL.24 (2) 2011 Table (1) :The physical properties for synthesized ligand (L) and its complexes D = decomposition Table (2): 13C-NMR chemical shifts for L-ascorbic acid, L (ppm in D2O) practically and theoretically are comptable Table (3) 1H-NMR, chemical shifts for L (ppm in D2O) Compounds H–4 H–5 O=C–OH Practical (L)  4.2 ppm 4.8 8–9.5 ppm No. Compound Colour M.PC or (D) Yield % C% H% M% Theo. Pract. solubility 1 L Orange 138-139C 85.7 (22.1) 21.5 (3.04) 3.08 Water, DMF, DMSO 2 [LCo.H2O].3H2O Dark red 118-120C 74 – – (16.80) 16.05 Water, DMF, DMSO 3 LNi.H2O Pale green 148-150C 88 – – 12.60 13.45 Water, DMF, DMSO 4 LCu.H2O Green 168-170C 80 – – (13.40) 14.22 Water, DMF, DMSO 5 LCd.H2O Pale brown 212-220D 82.2 – – (21.60) 22.30 Water, DMF, DMSO 6 [LPb.H2O].9H2O.3EtO H.4KCl White 218-220D 85 – – (16.60) 16.84 Water, DMF, DMSO 7 [LHg.H2O].9H2O.4KC l Pale brown 130-131D 80.3 – – (18.50) 18.30 Water, DMF, DMSO 8 [LCa.H2O].9H2O.5EtO H.3KCl. White 185-186C 61.6 – – (3.70) 3.80 Water, DMF, DMSO 9 [LMg.H2O].9H2O.5Et OH.4KCl White 100-101C 66 – – (2.10) 1.89 Water, DMF, DMSO Compounds C–1 C–3 C–2 C–4 C–5 C–6 C=O O–CH2 (Pract)L 173.74 156 118 76 69 62 177 42.8 IBN AL- HAITHAM J. FOR PURE & APPL. SCI. VOL.24 (2) 2011 Table (4): Characteristic vibrarational frequencies (cm –1 ) Located in the FT-IR of the ascorbic acid, L, and its complexes Compounds (O–H) (C– H) aliph. (C=O )  cm–1 asym.  sym. COO–  cm–1 (M– O) Additional peaks L-ascorbic ac id 3525(s) 3410(s) 3315(s) 3213(s) 2916(s) 1755(s) Lacton e 1319  (O2–H) enolic 1138(s), 1118(s), 1072(s), 1026(s) 987 (s) (C–O, C–C) ring L 3421(br) 2700- 2500 2954(w) 1755(s) (1608)s O=C–OH 1149, 1114, 1080, 1049, 941 (C–O– C), (C–C–C)  (1404), (1400) m (C–3–O) L complexes [LCo.H2O].3H2O 3417(br) 3383(br) 2958(w) 1730 25 (1500)w (1408)s 92 455 (1600)s C=O and C=C coupling (867-740)s coordinated water LNi.H2O 3414(s) 2950 1730 25 (1515)w (1408)s 107 443 (1608)s C=O and C=C (867-702)s coordinated water LCu.H2O 3425(br) 2962 1732 23 (1530)w (1419)s 111 439 (1635)s C=O and C=C (790– 666)s coordinated water LCd.H2O 3431(br) 2929 1741 14 (1530)w (1427)w 103 453 (1593)s C=O and C=C (773–570) coordinated water [LPb.H2O].9H2O.3EtOH.4K Cl 3441(br) 2920 1732 23 (1500)w (1411)s 89 420 (1593)s C=O and C=C (825-702)s coordinated water [LHg.H2O].9H2O.4KCl 3422 2943 1743 12 (1520)w (1425)w 95 441 (1598)br C=O and C=C (763-675)s coordinated water [LCa.H2O].9H2O.5EtOH.3K Cl. 3421 2958 1728 27 (1500)w (1408)s 92 459 (1597)s C=O and C=C (937-694)s coordinated water [LMg.H2O].9H2O.5EtOH.4 KCl 3352 3249 2966 1720 35 (1495)w (1408)s 87 455 (1600)s C=O and C=C (775-638)s coordinated water Recorder as KBr disk br = broad, s = strong, w = weak, m = medium,  = bending, aliph. = Aliphatic, asym. = asymmetric,  sym. = symmetric IBN AL- HAITHAM J. FOR PURE & APPL. SCI. VOL.24 (2) 2011 Table (5) Electronic spectral data of ligand (L) and its metal complexes Compounds  nm – wave number cm–1 mex molor–1 cm–1 Assignment bands Proposed structure L 246 40650 1175 * [LCo.H2O].3H2O 440 590 680 22220 16949 14706 110 650 600 T2g* 4T1gT1g(p) 4T1g4A2g octahedral LNi.H2O 656. 5 776 15232 12987 100 90 3A2g1Eg 3A2g3T1g(f) octahedral LCu.H2O 808 12376 662 2EgT2g octahedral LCd.H2O 300 400 33333 25000 500 200 L.F.C.T octahedral [LPb.H2O].9H2O.5EtOH.4 KCl 300 400 33333 25000 700 150 L.F.C.T octahedral [LHg.H2O].9H2O.4KCl 300 400 33333 25000 1300 750 L.F.C.T octahedral [LCa.H2O].9H2O.5EtOH.4 KCl 300 400 33333 25000 800 250 L.F.C.T octahedral [LMg.H2O].9H2O.5EtOH.3 KCl 300 400 33333 25000 1500 250 L.F.C.T octahedral L.F.C.T = Ligand Field Charge Transfer IBN AL- HAITHAM J. FOR PURE & APPL. SCI. VOL.24 (2) 2011 Table (6): VM, VL and Absorption of ligand (L), VM = volume of metal in ml, VL= volume of ligand in ml [L–Cd.H2O] [L–Co.H2O].3H2O VM VL Abs VM VL Abs 1 ml 0.25 1.315 1 ml 0.25 1.320 1 0.50 1.330 1 0.50 1.340 1 0.75 1.354 1 0.75 1.397 1 1 1.352 1 1 1.383 1 1.25 1.374 1 1.25 1.386 1 1.50 1.382 1 1.50 1.386 1 1.75 1.375 1 1.75 1.386 1 2 1.377 1 2.0 1.392 1 2.25 1.406 1 2.25 1.381 1 2.50 1.395 1 2.50 1.367 1 2.75 1.404 1 2.75 1.410 1 3 1.400 1 3.0 1.400 1 3.25 1.422 1 3.25 1.414 1 3.50 1.401 1 3.50 1.406 1 3.75 1.384 1 3.75 1.410 1 4 1.412 1 4 1.408 K= ML/ [M] [L] (1)  = (Am – As) / Am (2) K = The equation (1) is written to mol ratio (1:1) as the following KF = (1-)/  2 C (3)  = max.b.c (4) KF = stability constant  = Decomposition Degree M = Metal ion L = The ligand [ ] = concentration As = The absorption at the equivalent point of mole ratio Am = The maximum absorption of the mole ratio C = The complex concentration (mole. L –1)  G = – 2.303 RT Log K[22] R = 8.303 T = 273 + 25 = 298 IBN AL- HAITHAM J. FOR PURE & APPL. SCI. VOL.24 (2) 2011 Compounds As Am  K Log K 1/K G [LCd.H2O] 1.352 1.377 0.018 3×10 9 9.5 0.11 - 54.2 [LCo.H2O].3H2O 1.383 1.392 0.0065 2×10 9 9.3 0.11 - 53 [LCd.H2O]  [LCo.H2O].3H2O Table (7) :The absorbance values against mole– ratio values of complex [LCd.H2O] in solution (1×10 –3 mole.L –1 ) in water at ( 271 nm) No. L:M Absorbance 1 0.5:1 1.330 2 1:1 1.352 3 2:1 1.377 4 3:1 1.400 5 4:1 1.412 Table (8) :The absorbance values against mole– ratio values of complex [LCo.H2O].3H2O in solution (1×10 –3 mole.L–1) in water at ( 263 nm) No. L:M Absorbance 1 0.5:1 1.330 2 1:1 1.383 3 2:1 1.392 4 3:1 1.400 5 4:1 1.408 IBN AL- HAITHAM J. FOR PURE & APPL. SCI. VOL.24 (2) 2011 Table (9) The molar conductance of the complexes Compound fragment ions m S . cm 2 molar –1 Ratio [LCo.H2O].3H2O 141 1:1 LNi.H2O 24 Neutral LCu.H2O 113.5 1:1 LCd.H2O 6.6 Neutral [LPb.H2O].9H2O.5EtOH.4KCl 7 Neutral Table (10): Effect of ligand and its complexes on staphylococcus aureu a exherichia coli Compound 100 mg/ ml Diameter of inhibition zone (mm) at concentration 1 mg/ ml Staphylococcus Escherichia coli L 27 26 L Cd 25 22 L Cu 24 24 L Ca 0 0 IBN AL- HAITHAM J. FOR PURE & APPL. SCI. VOL.24 (2) 2011 Fig. (1): The IR of L-ascorbic acid Fig. (2):The IR of the ligand (L) 2,3,5,6-O,O,O,O-tetraacetic acid L-ascorbic acid Fig. (3) The IR of LCo IBN AL- HAITHAM J. FOR PURE & APPL. SCI. VOL.24 (2) 2011 Fig. (3a): The mass spectrum of (L) Fig. (4) suggested structure of (LM +2) Fig. (5a): 1H-NMR for the ligand L Fig. (5b): 13C-NMR for the ligand L O O M O O OH2 O O C C H2CO O CH2CO H O O C O H O H O H2 CH H H2C H 3 1 2 4 6 5 M+2 = Co, Ni, Cu, Cd, Pb, Hg, Ca, Mg IBN AL- HAITHAM J. FOR PURE & APPL. SCI. VOL.24 (2) 2011 Fig. (6) The U.V of the ligand (L) Fig. (7) The U.V of LCo IBN AL- HAITHAM J. FOR PURE & APPL. SCI. VOL.24 (2) 2011 Fig. (8): The mole ratio curve of complex [LCd.H2O] in solution (1×10 –3 mole. L–1) at ( = 271 nm) Fig. (9) :The mole ratio curve of complex [LCo.H2O].3H2O in solution (1×10–3 mole. L–1) at ( = 263 nm) 0 5 10 15 20 25 30 35 40 45 50 Ca Cu Cd L Concentration of ligands and its complexes (1mg/ml) D im et er o f in h ib it io n z on e (m m ) 0 5 10 15 20 25 30 35 40 45 50 Ca Cu Cd L D im et er o f in h ib it io n z on e (m m ) Concentration of ligands and its complexes (1mg/ml) IBN AL- HAITHAM J. FOR PURE & APPL. SCI. VOL.24 (2) 2011 Fig. (10): Effect of staphylococcus gram positive Fig. (11): Effect of Escherichia coli gram negative 2011) 2( 24المجلد مجلة ابن الھیثم للعلوم الصرفة والتطبیقیة تحضیر ودراسة طیفیة وبایولوجیة لبعض المعقدات الفلزیة مع 2,3,5,6-O,O,O,O رباعي حامض الخلیك-L-حامض اسكوربك جاسم شهاب سلطان،عبد الجبار عبد القادر مخلص، فالح حسن موسى ابن الهیثم،جامعة بغداد-كلیة التربیةقسم الكیمیاء، 2010آب 11:استلم البحث في 2011شباط 8: قبل البحث في الخالصة L اجدیـد ااسكوربك مع كلورو حامض الخلیك بوجـود هیدروكسـید البوتاسـیوم معطیـًا لیكانـد-Lدرس تفاعل حامض )2,3,5,6-O,O,O,O ربـاعي حـامض الخلیـك-L-تحلیـل العناصـر : ألتیـةطة التقنیـات اابوسـ، وشـخص )حـامض اسـكوربك )H, C( ،ة، -األشـعة فـوق البنفســجیةو ، األشـعة تحـت الحمــراء ة مـع طیـف الــرنین النـووي المغناطســيو المرئیـ -طیـف الكتلــ .13Cوالكاربون 1Hالبروتون ، Co ،Ni ،Cu ،Cd ،Pb(كما حضرت وشخصت منه معقدات أمالح بعض ایونـات العناصـر الثنائیـة التكـافؤ Hg ،Ca ،Mg.( ـــراء، لمعاســـت ــعة تحـــت الحمـ ــات طیــــف األشـ ــعة فـــوق البنفســــجیةو ت تقنیـ ـة، التوصـــیلیة الكهربائیــــة، -األشـ والمرئیــ االمتصاصیة الذریة، والنسبة المولیة لمعقدات الكادمیوم والكوبلت، واسـتنتج مـن التحالیـل ان تناسـق ایـون الفلـز الثنـائي التكـافؤ ـاني معطیــًا شــكال O–2–O–CH2COOH ،O–6–O–CH2COOH، )كتــونال( C–1=Oمــع اللكانــد مــن خـــالل ثمــ تكمــا درســ. لمعقــدین الكوبلـت والنیكــل للمعقــدین الكوبلــت والكـادمیوم وحســاب  ،Kf ،maxقـیم توقــد حســب. السـطوح ـادمیوم، الكالسـیوم(ومعقداتـه Lالفعالیـة البایولوجیـة للكانــد ة تجــاه )النحـاس، الكـ ا فعالیــة متباینـ ، وقـد أظهــرت النتـائج امتالكهـ Staphylococcus aureu وEscherichia coli ـا الــذي مــا عـــدا معقــد الكالســیوم ة تجــاه البكتریــ لـــم یظهــر أي فعالیــ .المذكورة أعاله وجیة تحضیر ،مطیافیة ، الدراسات البایول: الكلمات المفتاحیة