IBN AL- HAITHAM J. FOR PURE & APPL. S CI. VOL.23 (2) 2010 Synthesis and antibacterial study of the ligand type Schiff base derived from amino acid [L- Phenylalanine] and its complexes with Co (II), Ni (II), Cu (II) and Zn (II) ions M. R. Aziz Departme nt of Chemistry, College of Education, I bn-Al-Haitham, Unive rsity of Baghdad Abstract L-Pheny lalanine amino acid was condensed with 2-hy droxy bezaldehy de to give the Schiff b ase sodium 2-(2-hy droxy benzy lideneamino)-3-phenylprop anoate, which was used as a p recursor [NaHL]. The p recursor was reacted with 1,2-dichloroethane to give the Schiff base sodium 2,2'-(2,2'-(ethane-1,2diylbis(o xy ))bis(2,1-p heny lene))bis(methan-1-y l-1-ylidene)bis(azan- 1-y l-1-y lidene)bis(3-p henyl p rop anoate), which was used as a ligand [Na2L], in comp lexation with some metal (II) chloride M Cl2, where [M = Co(II), Ni(II), Cu(II) and Zn(II)], t o give [M (L)] comp lexes. The [Na2L] ligand and All complexes were characterized by sp ectroscop ic methods, [FT IR, UV-Vis, atomic absorp tion], melting p oint, chloride content, conductivity and magnetic susceptibility measurements, as well as the Na2L ligand characterized by 1 H NM R. The data, of these studies and measurements were imp ortant t o suggest an octahedral geometry around Co(II), Ni(II), Cu(II) and Zn(II) ions. The sy nthesized ligand, alon g with its metal comp lexes, was screened for in vitro antibacterial activity against gram-p ositive bacteria lik e Staphylococcus aureus, and Acinetobacter baumannii. This st udy showed an effective inhibition of gram- p ositive bacteria. Introduction Schiff b ases have been used as chelatin g ligands in the field of coordin ation chemistry and their metal comp lexes are of great interest for many y ears [1]. Chemists have rep orted on the chemical, st ructural and biological p rop erties of Schiff b ases, Schiff b ases are char acterized by the -N=CH- (imine) group which is imp ortant in elucidatin g the mechanism of transamination and rasemination reaction in biolo gical sy st em [2, 3]. Schiff base metal comp lexes have b een widely studied because they have industrial, antifungal, antibacterial, anticancer and herbicid al applications [4, 5]. They serve as models for b iolo gically imp ortant species and find app lications in bio mimetic catalytic reactions, Schiff bases are active against a wide range of or ganisms, for example; Candida Albicans, Escherichia coli Staphy lococcus aureus, Bacillus p oly mxa, the Try chophyton gyp seum. Ant ibacterial activity has been st udied more than antifun gal activity , because bacterium can achieve resistance to antibiotics through bioch emical and morphological modifications [6, 7]. Ch elatin g ligands containin g N, S and O donor atoms showed a broad biolo gical activity and are of sp ecial interest because of the variety of way s in which they are bonded to metal ions. It is known that the existence of metal ions bonded to biolo gically active comp ounds may enhance their activities [8-10]. T he aim of the present study is to sy nthesis, IHJPAS IBN AL- HAITHAM J. FOR PURE & APPL. S CI. VOL.23 (2) 2010 characterize and evaluate the metal co mplexes as antibacterial agent as p romising addition of new class of complexes as metal b ased drugs. Experime ntal The used chemicals were of analy tical gr ades; metals were used as chlor ide salts. The comp lexes were id entified by atomic absorp tion technique, usin g Schimadzu (A.A) 680 G atomic absorption sp ectrop hotometer. I.R data were r ecorded as (KBr) d isc usin g Schimadzu 4800 S FT IR sp ectrop hotometer in the range (4000-400) cm -1 . 1 H NM R sp ectra were recorded in DM SO- d6 using Brucker 300 MHz sp ectrometer. (UV-Vis.) sp ectra were obtained in (M eOH) on a CECIL, CE 2700 sp ectrop hotometer in the range (200-900) nm usin g quartz cell. The M agnetic measurements were carr ied out on solid comp ounds using 6 Bruker B.M instrumental. M elting p oints were recorded on an electro thermal Stuart apparatus and are uncorrected. Electrical conductivity measurements of the comp lexes were recorded at 25C˚ for 10 -3 M solutions in (M eOH) as a solvent using a Wissenchaftilich tecchnich werkst taten, D1820 bweilheimI.F 42 conductivity meter. Chloride contents for comp lexes were determined p otentiometerically by using (686-titro p rocessor-665), Dosinat-metrom Swiss. Antibacterial screen ing was used agar diffusion technique [11,12]. Preparation of the ligand [Na2L] The ligand was p repared by two steps S tep (1): L-p heny lalanine (1 g, 6.0 mmol), was added to (10 ml), (0.24g, 6.0 mmol) sodium hy droxide-methanol solution, the mixture was st irred until a clear solution was obtained. A solution of (0.74 g, 6.0 mmol) of 2-hy droxy bezaldehy de in (10ml) methanol was added to reaction mixture, which was cataly zed with (5drops) of glacial acetic acid and st irred for (3 hours). Yellow p recipitate was formed, filtered, washed with ethanol, and r e-cry st allized from hot methanol to give yellow cryst als of the precursor [NaHL], Yield (67%), mp (225-232˚C). S tep (2): A solution of the p recursor [NaHL] (2.35g, 8.08mmole) in (10 ml) methanol was added to (10ml), (0.45 g, 8.08 mmol) p otassium hy droxide-methanol solution, then a solution of (0.4 g, 4.04mmole) of 1,2-dich loroethane in (10ml) methanol was added to reaction mixture was reflu xed with stirring for (3 hours). Orange precipitate was formed, filtered, washed with ethanol, and re-cryst allized from hot methanol t o give or ange cryst als of t he ligand [Na2L], Yield (72%), mp (260-266˚C). Preparation of [Na2L] complexes with metal ions A solution of (0.08g, 0.33mmole) of [Na2L] ligand in methanol (5ml) was added to stirred clear solution of a solution of (0.2g, 0.33mmo le) of CoCl2.6H2O in (5ml) methanol. R eaction mixture was reflu xed for (4 hours); dark-brown p recipitate was formed, filtered and washed by water and re-cry st allized with ethanol. The comp lexes [Ni(L)], [Cu(L)] and[Zn(L)], were obtained in a similar method to that mentioned in the prep aration of [Co(L)] comp lex described above. Phy sical prop erties of the p rep ared comp lexes were given in (Table 1). Results and Discussion Synthesis of the ligand The ligand [Na2L] was p repared accordin g to the gener al method shown in (scheme 1). The I.R sp ectral analysis of the precursor [NaHL], (Table 2), showed phenolic (–OH) band at (3433) cm -1, and υ(C=N) bands at (1638) cm-1, also the sp ectrum showed bands at (1519) cm-1, and (1404) cm -1 which assi gned to υas(COO - ) and υs(COO - ) resp ectively and showed band at (1149) cm -1 which can be attributed to υ(C-O)p henolic group [13-17], by comp aring with the I.R sp ectral IHJPAS IBN AL- HAITHAM J. FOR PURE & APPL. S CI. VOL.23 (2) 2010 analysis of the ligand [Na2L], Fi g(1), (Table 2), showed bands at (1635) cm -1 which assigned to υ(C=N) and band at (1219) cm -1 which assigned to ether group (C-O-C), also the sp ectrum showed bands at (1539) cm -1 , (1404) cm -1 which assigned to υas(COO - ), and υs(COO - ) resp ectively [13-17]. Electronic sp ectral analy sis of the p recursor [NaHL], (Table 3), showed four absorp tion p eaks at (231.5) nm εm ax (2426) molar -1 cm -1 , (248.5) nm εm ax (2503) molar -1 cm -1 , (316.1) nm εm ax (1149) molar -1 cm -1 and (404.3) nm εm ax (777) molar -1 cm -1 , which assigned to (π→π * ), (π→π * ), (n→π * ) and (n→π * ) transition resp ectively [18,19]. by comp aring with electronic sp ectral analysis t he ligand [Na2L], Fig(2), (Table 3), showed four absorp tion peaks at (236.0) nm εm ax (2395) molar -1 cm -1 , (259.0) nm εm ax (2501) molar -1 cm -1 , (319.2) nm εmax (1129) molar -1 cm -1 , and (407.5) nm εm ax (697) molar -1 cm -1 , which assi gned to (π→π * ), (π→π * ), (n→π * ) and (n→π * ) transition resp ectively [18,19]. 1 H NMR sp ectral analysis of the ligand [Na2L], Fig(3), showed chemical shifts δ (pp m) of Schiff b ase proton (-CH=N-) at (7.9) as a singlet p eak. A multip le sign als at rings (6-7 and 7-7.5)pp m for phenylalanine p roton and phenyl-ether proton. (-CH) p roton of (-C=N-CH-) group at [3.7, 1H, t], (-CH-) methelene group at [3.4, 2H, d], and triplet p eak at (4.4)pp m, which assigned to (-CH2-) in (Ph-O-CH2-) group . A singlet high p eak at (4.9)pp m for the trace M eOH solvent [14,15,20,21] . Synthesis of the complexes Complexation of ligand [Na2L] with Co(II), Ni(II), Cu(II) and Zn(II) were carried out in M eOH. T hese comp lexes are st able in solution. The analytical and p hy sical data (Table 1), and sp ectral data (Table 2, and 3), are comp atible with the suggested st ructure (Scheme 1). The I.R sp ectra of the comp lexes [Co(L)](1), Fi g(4), [Ni(L)](2), ([Cu(L)](3)) and [Zn(L)](4), (Table 2), exh ibited the band at (1635) cm -1 in the fr ee ligand sp ectrum which assi gned to υ(C=N) imine group Shifted to lower frequen cy and appeared at (1619) cm -1 , (1614) cm -1 , (1617) cm -1 and (1614) cm -1 for the comp lexes (1),(2),(3), and (4) resp ectively [15-18]. These bands were assigned the υ(C=N) st retches of reduced bond order, this can be attributed to the delocalization of metal-electron density into the ligand π-sy stem (HOMO→LUM O) [22, 23], (HOM O=Highest occup ied molecular orbital, LUM O= Lowest unoccup ied molecu lar orb ital). The ether (C-O-C) st retching vibration app eared at (1219) cm -1 in the free ligand was Shifted to high er frequency and app eared at (1311) cm -1 , (1300) cm -1 , (1300) cm -1 and (1292) cm -1 for the comp lexes (1),(2),(3), and (4) resp ectively, all that indicated a linkage b etween o xy gen of ether group and the metal [14, 22], also t he sp ectrum showed bands at (1539) cm -1 , (1404) cm -1 which assigned to υas(COO - ), and υs(COO - ) resp ectively in the free ligand sp ectrum, was shifted to lower frequency and ap p eared at [(1496), (1350)], [(1486), (1377)], [(1450), (1369)] and [(1480), (1373)] cm -1 for the comp lexes (1),(2),(3), and (4) resp ectively, all that indicated a linkage between o xy gen of carbo xy late group and the metal [24,25]. The sp ectra showed the app earance of bands at (460) cm -1 , (482) cm -1 , (478) cm -1 and (474) cm -1 refer to υ(M -N) for comp lexes (1),(2),(3), and (4), these bands confirm the coordination of the nitrogen atom to the metal center, while t he bands at (576) cm -1 , (563) cm -1 , (574) cm -1 and (568) cm -1 assigned to υ(M -O) of comp lexes (1), (2), (3) and (4) resp ectively, bands confirm the coordination of the oxy gen atom of carboxy late group of the ligand to metal center, and the bands at (547) cm -1 , (532) cm -1 , (543) cm -1 and (536) cm -1 assigned to υ(M -O) of complexes (1),(2),(3), and (4) resp ectively, theses bands indicating that t he etheric o xy gen in the ligand is involved the coordin ation with metal ions in comp lexes [22-23, 26,27]. Electronic sp ectral analy sis of t he complexes, (Table 3): Comple x[Co(L)]: showed two high intense p eaks at (245.5) nm εm ax (2642) molar -1 cm -1 and (268.6) nm εm ax (2532) molar -1 cm -1 wer e assi gned to the ligand field, while a med ium p eak at (382.0) nm εmax (943) molar -1 cm -1 was assigned to (C.T), a weak broad peaks at (491.2) nm εm ax (62) molar -1 cm -1 ,(531) nm εm ax (56) molar -1 cm -1 , and (622.0) nm εm ax (16) molar -1 cm -1 , were IHJPAS IBN AL- HAITHAM J. FOR PURE & APPL. S CI. VOL.23 (2) 2010 assigned to (d-d) electronic transition ( 4 T1g(F)→ 4 T2g(F)), ( 4 A2(g)→ 4 T1g), and ( 4 T1(g)→ 4 T1g(p)) resp ectively, suggesting o ctahedral geometry [19]. Comple x [Ni(L)]: showed one high intense absorp tion at (245.5) nm εm ax (2613) molar -1 cm -1 are due to the ligand field, another high intense p eak at (364.5) nm εm ax (1825) molar -1 cm -1 was assigned to (C.T), while a weak broad peaks at (450.6) nm εm ax (49) molar -1 cm -1 , (510.4) n m εm ax (22) molar -1 cm -1 , and (642.5) nm εm ax (17) molar -1 cm - were assign ed to (d-d) electronic transition ( 3 A2g→ 3 T2g), ( 3 A2g→ 3 T1g), and ( 3 A2g→ 3 T1g(p)) resp ectively, suggesting octahedral geometry [19]. Comple x [Cu(L)]: Fig(5), showed two high intense absorp tion peaks at (243.0) nm εm ax (2624) molar -1 cm -1 , and (272.1) n m εm ax (2543) molar -1 cm -1 are du e to the ligand field, a h igh intense absorption peak at (369.0) nm εm ax (1831) molar -1 cm -1 was assigned to (C.T ), while a weak broad p eak at (660.5) nm εmax (41) molar -1 cm -1 was assigned to (d-d) electronic transition ( 2 E→ 2 T2) suggesting o ctahedral geometry [19]. Comple x [Zn(L)]: showed two p eaks at (242.0) nm εm ax (2537) molar -1 cm -1 and (272.0) n m εm ax (2315) molar -1 cm -1 are due to the ligand field. While a high intense p eak at (361.0) nm εm ax (1763) molar -1 cm -1 was assi gned to (C.T), the d 10 configur ation of Zn II ion alon g with the data obtained confirms a o ctahedral structure around the ion [19]. The molar conductance of the co mplexes in methanol lie in the ran ge (5.1-12.9 Ohm -1 cm - 2 mol -1 ), (Table 3), indictin g their non- electroly te having mole ratio of metal:ligand as 1 :1 [28]. At the room temp erature magnetic moments of the all comp lexes showed normal magnetic moment in (Table 3), the magnetic moment data were ca. (4.13), (3.25) and (1.65) B.M for Co(II) in [Co(L)], Ni(II) in [Ni(L)], Cu(II) in [Cu(L)], r esp ectively and (0.00) B.M to Zn(II) in [Zn(L)]. The magn etic moment studies showed that these complexes were octahedral geometry [29]. Biological activity The antibacterial activity of the sy nthesized ligand [Na2L] and its comp lexes [Co(L)](1) , [Ni(L)](2), [Cu(L)](3), and [Zn(L)](4) (Table 4 and 5 ), were tested utilizing the agar diffusion technique [30]. The organism tested was staphylococcus aureus, and Acinetobacter baumannii. The agar media were inoculated with test organisms and a solution of the tested comp ound (100μg/ml) was p laced sep arately in cups (6 mm diameter) in the agar medium. The inhibition zones were measured after 24 hours incubation. Separate st udies were carried out with the solution alone of DM SO and the showed no activity against any bacterial st rains [31]. T he results of these st udies revealed that the ligand and metals comp lexes showed an effective in the inhibition of Acinetobacter baumannii and Staphylococcus aureus. Biological activity of the p revious compounds in inhibition of bacterial growt h could be att ributed to one of the following mechanisms, the first mechanism is by the inhibition of the bacterial cell wall sy nthesis by bounding to the p recursor of the cell wall, and second mechanism revealed that some antibodies have similar st ereo st ructure to substrate (D-alany l D-alanine). So it will act comp etitive inhibitions for t he enzy mes (t ransp eptidase and /or carboxp eptidase) which are the main enzy mes cataly zed the end st ep in the biosy nthesis of p eptidoglycans of the bacterial cell wall, other mechanisms could contributed to the results found in the st udy which include the inhibition of biosy nthesis of bacterial p roteins by linking to the ribosome by doing so, t he ribosome will not be in contact with tRNA (transfer ribonucleic acid) , so the bacteria will not survive, an other mechanisms were p ost ulated that some antibodies inhibit t he denovo sy nthesis of bacterial DNA by sp litting DNA in DNA-enzy me comp lexes by inhibition DNA ligase [32-34]. Re ferences 1- Lotf ,A. Saghatforoush 1, Ali Aminkhani , Sohr ab Ershad , Ghasem Kar imnezhad , Shahriar Ghammamy and Roya Kabiri, (2008), “Preparation of Zinc (II) and Cadmium (II) Complexes IHJPAS IBN AL- HAITHAM J. FOR PURE & APPL. S CI. VOL.23 (2) 2010 of the Tetradentate Schiff Base Ligand 2-((E)-(2-(2-(py ridine-2-yl)- ethy lthio)ethy limino)methy l)-4-bromop henol (Pyt BrsalH)”, M olecules, 13: 804-811. 2- Lau, K. Y. ; M ayr, A.; Cheung, K. K., (1999), "Sy nhesis of transition metal isocyanide comp lexes containin g hy drogen bonding sites in p erip heral locations", Inorg. Chim. Acta, 285: 223-232. 3- Shawali, A. S.; Harb, N.M .S.and Badahd ah, K. O., (1985), "A st udy of tautomerism in diazonium couplin g p roducts of 4- hy roxy coumrin", J. Heterocy lylic Chem., 22: 1397-1403. 4- Cozzi, P.G. M etal–Salen Schiff base comp lexes in cataly sis: Practical asp ects. (2004), Chem. Soc. Rev. 33 : 410-421. 5- Chandra, S.; Sangeetika, J., (2004), EPR and electronic sp ectral studies on copp er (II) comp lexes of some N-O donor ligands J. Indian Chem. 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P., (1968)."Inorganic electronic sp ectroscopy ”, New y ork . 6, 121, IHJPAS IBN AL- HAITHAM J. FOR PURE & APPL. S CI. VOL.23 (2) 2010 20- Bellamy,L. J. (1975)."The Infrared sp ectra of comp lexmolecules",Hasted p ress,Division of John Willey and Sons, Inc.,New y ork, 21- Coop er,J.W., (1980), "Sp ectroscop ic Techniques for or ganic Chemist ry",John Willey and sons, New York. 22- Nakamoto, (1996), "Infrared sp ectra of inorganic and coordination comp ound" 4 th ed. J. Wiely and sons, New York. 23- Agarwal,R. K.; Prased, S. and Gahlot. N. (2004), “Sy nthesis, sp ectral and thermal p rop erties of some penta-coordinated comp lexes of o xov anadium(IV) d erived from thiosemicarbazones of 4-aminoantipy rine,” Turkish Journal of Chemistry , 28: ( 6) 691–701. 24- Pavel Kop el , M artin Biler , and M ilan Nadvornik, (1998), " Iron (Ш) Salen and saloph Schiff bases bridged by dicarboxy lic acids " , Chemica 37 ,. 25- WEI Dany i, LI Nin g, LU Gui & YAO Kemin, (2006), ” Sy nthesis, cataly tic and biolo gical activity of novel dinuclear copp er comp lex with Schiff base”, Science in China: Series B Chemistry , 49 : (3) 225—229. 26- Raju ,K. C. and Radhakr ishan, P. K. (2003), "complexes of copp er with 2,3-dimethy l-4- formyl(benzhy drazide)-1- p heny l-3-pyrazolin-5-one" sy nthesis and reactivity in inorganic and metal – or ganic chemistry , 33 : (8 ) ,1307-1318. 27 - Greenwood ,N. N. and Earnshow ,A., (1998), "Chemistry of the elements," J. Wiely and sons Inc. New York. 28- Geary, W. J. (1971), “The use of conductivity measurements in or ganic solv ents for the characterization of coordin ation comp ounds”, Coord. Chem. Rev. 7:81-115. 29- Huheey,J. E., (1994), "Inor ganic Chemist ry : Princip les of Stracture and Reactivity " Harp er International Edition, Harp er and Row p ublishers, New York. 30- Ali, M .M, Ismail M .M .F., Al-Gaby M .S.A., Zahram M .A., and Ammar Y.A. (2000), M olecules, 5:864-873. 31- Zahid, H. ;Choton , M .; Arif , M uhammed A. ;Akhtar and Claudiu, T. sup uran, ( 2006), "M etal-Based Ant ibacterial and Ant ifungal A gents:Sy nthesis, Characterization, and In Vitro Biolo gicalEv aluation of Co(II), Cu(II), Ni(II), and Zn(II) ComplexesWith Amino Acid-Derived Compounds" Bioinorganic Chemist ry , 5: 3. 32- Baron, E. J.; Chang, R. S.; Howed, H. D., k, (1994), “M edical M icrobiolo gy ", Wiely Liss., Publication, New York. 33- M urray ,P. R.; Baron , E. J.; Faller , M . A. P.; Tenover ,.F. C.; Yken, R. H. 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VOL.23 (2) 2010 Table (1): The microanalysis results and some physical propertie s for the ligand [Na2L] and its complexes dec. = decomp ose Table (2): Infrared spectral data for the ligand [Na2L] and its metal complexes cm -1 Compounds Formula Colour M.p (˚ C) Yield% Chlo ride content Metal M . wt Na2L C34H30N2Na2O6 Orange 26 0-266 72 Nil ----- 60 8.59 [Co(L)](1) C34H30 N2O6Co Dark brown 28 5 dec. 81 Nil 8.8 3 (9.48 ) 62 1.54 [Ni(L)](2) C34H30 N2O6Ni Light g reen 27 9 dec. 79 Nil 8.8 0 (9.45 ) 62 1.31 [Cu(L)](3) C34H30 N2O6Cu Dark green 29 1 dec. 84 Nil 9.4 5 (10.15) 62 6.16 [Zn(L)](4) C34H30 N2O6Zn Yellowish Brown 27 4 dec. 68 Nil 9.7 0 (10.42) 62 8.02 Compound υ(C= N) υ(O– H) υ a s(COO) υ a(COO) υ(C= C) Ar omatic υ(C–H) Ar omatic υ(C–H) Aliphatic υ(C– O–C) et heric υ(M – O) et heric υ(M -O) Car boxylate ion υ(M – N) Na HL 1638 3433 1519 1404 1585 3028 2939 -- --- -- -- -- -- -- -- Na 2 L 1635 -- --- 1539 1404 1589 3028 2947 1219 -- -- -- --- -- -- [Co(L) ]( 1) 1619 -- --- 1496 1350 1590 3028 2924 1311 547 576 460 [Ni(L)](2) 1614 -- --- 1486 1377 1587 3028 2931 1300 532 563 482 [Cu(L) ]( 3) 1617 -- --- 1450 1369 1587 3028 2924 1300 543 574 478 [Zn( L)]( 4) 1614 -- --- 1480 1373 1590 3024 2924 1292 536 568 474 IHJPAS IBN AL- HAITHAM J. FOR PURE & APPL. S CI. VOL.23 (2) 2010 Table (3): Electroni c spectral data for the ligand [Na2L] and its metal complexes Compound λ nm εmax mola r-1 cm-1 Assig nment Ratio Molar conductivity S.cm2.mo l-1 Magnetic sus ceptibility B .M coordina tio n NaHL 231 .5 248 .5 316 .1 404 .3 2426 2503 1149 777 π→π * π→π * n→π* n→π* ----- ------- ------ ------ Na2L 236 .0 259 .0 319 .0 407 .5 2395 2501 1129 697 π→π * π→π * n→π* n→π* ----- ------- ------ ------ [Co(L)](1) 245 .5 268 .6 382 .0 491 .2 531 .0 622 .3 2642 253 2 943 62 56 16 Ligand field Ligand field C.T 4T1g(→ 4T2g 4A2g→ 4T1g 4T1g→ 4T1g ( p) neutral 8.7 3.8 7 (4.13) Oct ahedral [Ni(L)](2) 245 .5 364 .5 450 .4 510 .4 642 .5 2613 1825 49 22 17 Ligand field C.T 3A2g→ 3T2g 3A2g→ 3T1g 3A2g→ 3T1g(p) neutral 5.1 2.8 3 (3.25 ) Octahedral [Cu(L)](3) 243 .0 272 .1 369 .0 660 .5 262 4 2543 1831 41 Ligand field Ligand field C.T 2E→2T2 neutral 5.6 1.7 (1.65 ) Octahedral [Zn(L)](4) 242 .0 272 .0 361 .0 2537 2315 1763 Ligand field Ligand field C.T neutral 12.9 Diamagnetic Octahedral IHJPAS IBN AL- HAITHAM J. FOR PURE & APPL. S CI. VOL.23 (2) 2010 Tab le (4): B iological activity of the ligand [Na2L] an d its metal complexes against Acinetobacter baumannii bacteria A= Acinetobacter baumannii bacteria Tab le (5): Biological activity of the ligand [Na2L] and its metal complexes against Staphylococcus aureus bacteria S= Staphylococcus aureus bacteria Compound Bacteria (zone of inhibition (diame ter mm)) A1 A2 A3 A4 A5 A6 A7 A8 A9 A1 0 Na 2 L 13 10 14 15 14 15 13 14 14 14 [Co(L) ]( 1) 13 9 8 16 16 16 13 13 11 15 [Ni(L)](2) 15 9 14 16 16 17 13 Nil 13 17 [Cu(L) ]( 3) Nil 9 14 14 13 14 12 Nil Nil 15 [Zn( L)]( 4) 10 10 12 13 13 17 Nil Nil 12 12 Compound Bacteria (zone of inhibition (diameter mm)) S1 S2 S3 S4 S5 S6 S7 S8 S9 S10 Na 2 L Nil 9 Nil Nil Nil Nil Nil Nil Nil Nil [Co(L) ]( 1) Nil Nil Nil Nil Nil Nil 12 Nil Nil 11 [Ni(L)](2) Nil Nil Nil Nil Nil Nil Nil Nil Nil Nil [Cu(L) ]( 3) Nil Nil 14 Nil Nil Nil Nil 8 Nil Nil [Zn( L)]( 4) Nil Nil 15 16 Nil Nil Nil Nil Nil Nil IHJPAS IBN AL- HAITHAM J. FOR PURE & APPL. S CI. VOL.23 (2) 2010 S cheme (1): Preparation of the ligand [Na2L] and its metal complexes C H O H N H C H 2 C C O O N a 2 - [ (2 - h y d r o x y b e n z yl id e n e) a m in o ] - 3 -p he n y lp r o p a n o ic a ci d C H 2 CH O O C N H 2 + C H O O H H + 2 -A m i no - 3 - ph e n yl - pr o p i o ni c ac i d 2 - H y d r ox y - be n z al de h y de S o d i um h yd ro x id e M et ha n o l , m ag n et ica ll y s ti rr i n g 3 h ou rs C H 3 C O O H ( 5 d r op s ) + M C l 2 M e t h a n o l R e f l u x 4 H o u r s M = C o ( I I ) ,N i ( I I ) , C u ( I I ) , a n d Z n ( I I ) N a O H C H O H N H C H 2 C C O O N a 2 + C l C H 2 C H 2 C l d i c h l o r oe t h a n e C H N H C H 2 C O C H O N C H H 2 C H 2 C H 2 C C O O N a C O O N a s o d i u m 2 , 2 '- (2 ,2 ' -( e t h a n e - 1 , 2 - d i y l b i s (o x y )) b i s (2 , 1 - p h e n y l e n e ) )b i s (m e t h a n - 1 - y l - 1 -y l i d e n e ) b i s(a z a n -1 -y l - 1 - y l i d e n e )b i s (3 - p h e n y l p ro p a n o a t e ) C H N H C H 2 C O C H O N C H H 2 C H 2 C H 2 C C O O N a C O O N a R e f l u x 3 H o u r s M e th a n M e t h a n o l K O H C H N C H O C H O N C H H 2 C H 2 C M H 2 C C O - O C H 2 C O O - IHJPAS IBN AL- HAITHAM J. FOR PURE & APPL. S CI. VOL.23 (2) 2010 Fig (1): Infrared spectrum of the ligand ( Na2L ) Fig. (2): Electronic spectrum of the precursor (Na2L) Fig. (3) 1 H NMR spectrum of the ligand (Na2L) IHJPAS Fig .(4): Infrared spectrum of the complex [Co(L)] IBN AL- HAITHAM J. FOR PURE & APPL. S CI. VOL.23 (2) 2010 Fig.(5): Electronic spectrum of the complex [Cu(L)] IHJPAS 2010) 2( 23المجلد مجلة ابن الهیثم للعلوم الصرفة والتطبیقیة المشتقة من نوع قاعدة شیفلیة البایولوجیة للیكاند من عاالفودراسة تخلیق مع األیونات ومعقداته )فنیل األنین-ل( حامض أمیني Co(II), Ni(II), Cu(II) and Zn(II) منهل ریمون عزیز جامعة بغداد ، كلیة التربیة أبن الهیثم ، قسم الكیمیاء خالصةال ل على قاعدة شیفللحصو زالدیهایدهیدروكسي بن-2 مع فنیل األنین -ل الحامض األمیني مفاعلة تضمن البحث Sodium2-(2-hy droxy benzy lideneamino)-3-phenylprop anoate التي أستعملت مـادة وسـطیة [NaHL] فتفاعل قاعدة شیأذ أعطى ال داي كلورو أیثان-1,2مع ثم مفاعلتها Sodium2,2'-(2,2'-(ethane-1,2'diylbis(oxy ))bis(2,1-p henylene))bis(methan-1-y l-1- y lidene)bis(azan-1-y l-1-ylidene)bis (3-p henyl p rop anoate) .والتي أستعملت كلیكاند [Na2L] ثم مفاعلة M]تكونـت معقـدات ذوات الصـیغة اذ، بعـض العناصـر الفلزیـة أیونـات یكانـد مـعالل (L)] ، M = Co(II), Ni(II), Cu(II), and Zn(II). الكمـي الـدقیق التحلیـلو المرئیـة –االشعة تحت الحمراء واالشعة فوق البنفسـجیة ،ق الطیفیة ائلمركبات بالطر شخصت جمیع ا خص و كـذلك شــ التوصــیلیة الموالریـة الكهربائیــة ومحتـوى الكلــور ودرجـة االنصــهار والحساسـیة المغناطیســیة ، و للعناصـر طة اسااللیكاند بو 1 H NM R . السطوح ثماني ي المقترح للمعقدات المحضرةمن نتائج البحث كان الشكل الفراغفأن . Staphylococcusال بكتریا موجبة لصبغة كرام درست الفعالیة البایولوجیة خارج الخلیة الحیة للیكاند ومعقداته ضد aureus وAcinetobacter baumannii ،ر مانع للبكتریا الموجبة لصبغة كرامتأثی أظهرت وجود و. IHJPAS