@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@Ü‹1a26@@ÖÜ»€a@I1@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (1) 2013 Synthesis, Spectroscopic and Biological Studies of a New Some Complexes with N-Pyridin-2-Ylmethyl-Benzene-1,2- Diamine Shaymaa H. Naji Lekaa K. Abdul Karim Falih H. Mousa Dept. of Chemistry/College of Education For Pure Science(Ibn Al- Haitham)/ University of Baghdad Received in :23 November 2011 , Accepted in 12 February 2012 Abstract N-Pyridin-2-ylmethyl-benzene-1,2-diamine (L) was prepared from the reaction of ortho amino phenyl thiol with 2 – amino methyl pyridine in mole ratio (1:1) . It was characterized by elemental analysis (C.H.N) , FT-IR , Uv – Vis , 1H , 13C-N.M.R . The complexes of the bivalent ions (Co , Ni , Cu ,Pd , Cd , Hg and Pb) and the trivalent (Cr) have been prepared and characterized too . The structural was established by elemental analysis (C.H.N) , FT-IR , Uv – Vis spectra , conductivity measurements , atomic absorption and magnetic susceptibility . The complexes showed characteristic behavior of octahedral geometry around the metal ions and the (N,N,N) ligand coordinated in tridentat mode except with Pd complexes showed sequare planer . α ,Kf,εmax for the complexes were estimated too. β for Co – complex was calculated . The study of biological activity of the ligand (L) and its complexes showed various activity toward staphylococcus aureus and E.coli. Key words : Synthesis ,Phenyl diamine , Complexes , Biological study , Bivalent ions. 193 | Chemistry @@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@Ü‹1a26@@ÖÜ»€a@I1@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (1) 2013 Introduction The macrocyclic compounds types N3 are considered to be a good coordinated ligands because involved hard nitrogen atoms as well as CoII , CuII[1,2] ,more over a greatest importance of tridentate ligands type N3 with variety substituents on the molecule and their complexes with metals , MgII and CaII in the metallic enzyme, blood protein[3] which contains cobalt ion and in the chlorophyll which contains MgII[4]. Recently complexes containing macrocyclic ligand type N3 donor atoms play a very important role in biological system such as CaII, FeII and PdII complexes[5] and high stable complexes of this type ligand with Tc, Re are used for radiopharmaceuticals applications[6,7] and in magnetic resonance imaging[8] ,also with NiII used as a catalyst for division DNA molecules and FeII complex with porphyrin as a model for biological proteins such as hemoglobin in blood[9]. This paper reports the synthesis and characterization of new ligand derived from the reaction of ortho amino phenyl thiol with 2 – amino methyl pyridine, the new ligand complexes with (CrIII,CoII,NiII,CuII,PdII,CdII,HgII and PbII) were prepared too. Experimental a. Chemicals ; All reagents were Analar or chemically pure grade by British Drug Houses (BDH) , Merk and Fluka . b. Materials : ortho amino phenyl thiol (C6H7NS),2 – amino methyl pyridine (C6N2H8) , cobalt chloride hexa hydrate (CoCl2.6H2O), Nickel chloride hexa hydrate (NiCl2.6H2O), copper chloride dihydrate (CuCl2.2H2O), Paladium chloride (PdCl2) ,Cadimum chloride dihydrate (CdCl2.2H2O) , Mercury chloride (HgCl2), Lead nitrate Pb(NO3)2 , Chromium trichloride hexa hydrate (CrCl3.6H2O) , Ethanol 99% (CH3CH2OH) , Dimethyl sulphoxide 99.5% (DMSO) , carbon tetra chloride 99.5% (CCl4) , chloroform 99% (CHCl3) and Toluene 99% (C7H8) . c. Instruments : -Elemental analysis for the new ligand (L) and complexes were determined by calibration type ; Linear Regression Euro EA Elemental Analysis were made in AL-Mustansiriyah University and Ministry of Science and Technology . -Melting points were determined by Gallen –Kamp apparatus . -'H,13C-NMR spectra were recorded in DMSO using BurKer 300 MHZ spectro meter at the AL-Albeit University Amman –Jordan . - FT-IR spectra were recorded as KBr discs in the range (4000 - 400 )cm-1 using Shimadzu- FT-IR . -UV-Visible spectra were recorded by Shimad Zu-UV-Vis -160 A Ultra Violet spectrophotometer at 25co ,using 1 cm quartz cell and examined at the range of (200 -1100 )nm at 10-3 M in Dimethyl sulphoxide. -Atomic Absorption (A .A) technique have been measured using ashimad Zu AA 680 G atomic absorption spectro photo meter in center of Ibn –Cina . -Molar conductivity of the complexes were measured on pw 9526 digital conductivity in Dimethyl sulphoxide at 10-3M . -Magnetic susceptibility were recoded by Magnetic susceptibility blance ,model ,MsB-MK1 in AL–Nahrain University . Preparation Synthesis of N-Pyridin-2-ylmethyl-benzene-1,2-diamine (L) Orthoaminophenyl thiol (0.125gm , 1mmol) and 2-amino methyl pyridine (0.10 gm , 1 mmol )in ethanol (10 cm3) was stirred for 3 hours . The precipitate was filtered and re- 194 | Chemistry @@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@Ü‹1a26@@ÖÜ»€a@I1@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (1) 2013 crystallized from hot absolute ethanol , fine yellow crystals were obtained ,m.p 83co ,yield 85% and it is soluble in most organic solvents as indicated in Table (1) . Synthesis of the metal complexes An ethanolic solution of the following metal salts Crcl3.6H2O(0.26gm,1mmol), CoCl2.6H2O (0.24gm,1mmol), NiCl2.6H2O (0.24gm,1mmol), CuCl2.2H2O (0.1gm,1mmol), PdCl2(0.17gm,1mmol), HgCl2(0.27gm,1mmol) and Pb(NO3)2(0.33gm,1mmol) were added to a solution of the ligand (L) (0.302 gm,1mmol) in ethanol . The mixture was strirred for 30min. The precipitate formed was filtered , washed with distilled water and dried under vacuum. Physical properties were given in (Table1) . Results and Discussion Synthesis and Physical properties of the ligand N-Pyridin-2-ylmethyl- benzene-1,2-diamine (L) . The ligand was obtained by the reaction of one mole of ortho amino phenyl thiol with one mole of 2 – amino methyl pyridine ; SH NH2 Orthoaminophenyl thiol + N NH2 2-(amino methyl) pyridine Ethanol 3h. NH2 N HN N-Pyridin-2-ylmethyl-benzene-1,2-diamine Elemental analysis (C.H.N) confirmed the purity of the ligand(L) with the formula C12H13N3 . The 1H,13C – NMR spectrum of the new ligand The 1H-NMR spectrum of the new ligand in DMSO(d6) at ambient temperature exhibit peak at 5.471ppm indicate the existence of amino group[10]. Other peaks around 6.42 – 7.11 ppm are related to aromatic hydrogens[11,12]. The13C – NMR spectrum showed two singlets at δ 133 and δ153 correspond to the carbons of the benzene ring that do not bear hydrogens .This leaves the signals δ117 and δ137 for carbon have one hydrogen.Singlet at δ 40 due to( – CH2 –) . Fig (1,2) showed chemical shifts δ(PPm) of the ligand (L) . The infrared spectrum of the ligand(L) The infrared spectrum of the ligand(L) in the solid state does not contain the(S-H) which appears in the starting material ortho amino phenyl thiol at (2600– 2500 ) cm-1 region .This indicates the displacement of SH in ortho amino phenyl thiol by means of (– NH – CH2 –) . Bands in the (3380,3290)cm-1, (1585) cm-1 and (1303)cm-1 are diagnostic of the primary aromatic amine[13,14].Fig(3)The infrared spectra of all complexes showed ,the multi bands in the range (3460 – 3282)cm-1 and split or broader band at (1604 – 1558) cm-1and (1303)cm-1 with the formation of a new absorption bands for the coordination through nitrogen atom[15,16] .(M – N) stretching vibration have been assigned in Table(2) . The bands characteristic of coordinated water and (M – O) are seen in complexes in the region (837 - 195 | Chemistry @@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@Ü‹1a26@@ÖÜ»€a@I1@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (1) 2013 817)cm-1and (563-545)cm-1[17].(Fig4). The pb complex spectrum exhibited bands at (933)cm-1,(663)cm-1 due to coordinate nitrate ion[18,19].(Table 2) describes characteristic stretching vibration frequencies (cm-1) located in the FT-IR of the ligand and its complexes . The UV –visible spectra of the ligand (L)and complexes The UV –visible spectra of the ligand (L)in DMSO solution exhibited strong absorption bands at (267nm,37453cm-1 ) and (313nm,31948cm-1 ), (353nm ,28328cm-1 ).Which are due to the π – π* and n – π* transition[20].Fig(5) The UV visible spectrum of Cr+3 complex showed one band in the region (580nm ,17241 cm-1 )is due to4A2 g 4T2 g[21] . The UV –visible spectrum of Co+2 complex showed bands in the region (800nm ,12500 cm-1 )due to 4T1 g 4T2g(F) ,(660 nm ,15151 cm-1 due to 4T1 g 4A2 g and (520nm ,19230 cm-1 ) due to 4T1 g(F) 4T1 g(p)[22,23] . The ratio of 19230cm-1 to 12500cm-1 is 1.54 which fits with Tanaba –Sugano d7 Curve (Fig6) for E/B=26 and ∆o/B'=16 . ∆o=12500cm-1 B' complex = 12500/16 = 781cm-1 B for free Co+2=971cm-1 β(nephelavetic effect) = B' complex / B Co+2 = 781/971 = 0.804 which indicates of d – electron delocalization on the ligand hence a significant covalent character in the complex[24] . The UV–Visible spectrum of Ni+2 showed one band at (825nm,12121cm-1) which is due to 3A2g 3T1g .Fig(7) Cu+2 complex appeared band at (660nm,15151cm-1) is due to 2Eg 2T2g . The brown palladium complex exhibited a strong band at (400nm ,25000 cm-1) due to 1A1g 1B1g transition[25] . The UV – Visible spectra of Cd+2,Hg+2 and Pb+2 complexes showed shifted bands compared with free ligand(L) are due to charge transfer (Table3) . The molar conductance of all complexes in DMSO were found to be low which suggested coordination of anion to the metal[21] . The μeff value of Cr,Co, Ni , Cu complexes are within the range (3.77,4.82 ,3.01,1.98) respectively expected for spin–free octahedral structures[26,27] . Electronic spectra , conductance in (DMSO) magnetic moment (B.M) of the ligand complexes are given in Table(3) . Study of Cr+3,Co+2,Ni+2,Cu+2complexes formation in solution The complexes of the ligand(L) with selected metal ions (Cr+3,Co+2,Ni+2,Cu+2) were studied in solution using ethanol as solvent , in order to determine (M:L) ratio in the prepared complexes , following molar ratio method[28] . A series of solution were prepared having a constant concentration (C) 10-3M of the hydrated metal salts and the ligand(L) . The (M:L) ratio was determined from the relation ship between the absorption of the observed light and the mole ratio (M:L) found to be (1:1) for all complexes . The results of complexes formation in solution are shown in (Table4,5,6,7 ) Vm = volume of metal in ml VL = volume of ligand in ml The stability constant (Kf) was evaluated using the following equations :- Kf = 1- α / α2c …… (1) α = Am-As /Am………(2) (α) is the degree of the dissociation , (c) is the concentration of the complex (10-3M) . (As) and (Am) are the absorbance value of the partially and fully formed complex respectively (Table8 ) . The absorbance of the solutions were measured at (λmax) of the maximum absorption . The molar absorptivity (εmax)(eq.3) has been calculated using equation; 196 | Chemistry @@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@Ü‹1a26@@ÖÜ»€a@I1@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (1) 2013 A = εmax . b . c ……. (3) (A) is the average of three measurement of the absorption containing the same amount of metal ion and three fold excess of ligand . (b) is the depth of the quartz cell usually equal 1 cm . The atomic absorption analysis was used to confirm the molar ratio calculation of [ metal : ligand](M:L) for the synthesis of complexes as well . The results showed a ratio M:L (1:1) for all complexes (Table 1) Biological activity study The biological activity of the prepared new ligand and its complexes were studied against selected types of micro organisums which include gram positive bacteria like staphylococcus aureues and gram negative bacteria like E.coli in agar diffusion method , which is used (DMSO) as asolvent . Agar diffusion method involves the exposure of the zone of inhibition toward the diffusion of micro organisms on agar plate . The plates were in cubated for (24) hrs. at (37co) The zone of inhibition of bacterial grouth around the disc was observed (Table9 ). Conclusion A series of complexes of Cr+3 ,Co+2, Ni+2 ,Cu+2 ,Pd+2 ,Cd+2 ,Hg+2 ,Pb+2 with N-Pyridin-2- ylmethyl-benzene-1,2-diamine (L)have been prepared and characterized . The tridentate ligand (L)(N,N,N)is binding metal ion forming octahedral structure except with pd is forming square planer as follows; N H2N NH CH2M X H2O X N H2N N CH2 Pd HCl Cl N H2N HN CH2M Cl Cl Cl M+3 =Cr M+2 =Pd M+2=Co,Ni,Cu,Cd,Hg X=Cl-1 M+2=Pb X=NO3-1 Biological effects of new ligand and its complexes indicated that the new ligand and its complexes exhibited antibacterial activity against both gram positive and gram negative bacteria . Refrences 1. Zolotov , Y.A.(1979)Macrocyclic compounds in Analytical chemistry , ed.2nd, New York. 2. Handel , I.L.; Muller ,R,N. and Gnglielmeti ,R.N. (1983)metal ions , Inorg chimi.,Acta 66(8):511-514. 3. Brow ,D.G.(1973)structure and spectroscopic study ,prig – Inorg. Chem. 13(8):177-180 . 197 | Chemistry @@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@Ü‹1a26@@ÖÜ»€a@I1@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (1) 2013 4. Warren , M.J. and Shah,H.N. ( 2000 ) biological study , Biolog. Chem. 221(21):421-430 5. Kimura , E.; Koike,T. ;Watanabe ,T.; Aoki , S. and Shiro , M.(1996) The modern structural theory of organic chemistry , J. Am.chem. 14(112):210-217 . 6. Naji, S.H.; Fathel ,H.A. and Musa ,F.H. ( 2008) Synthesis characterization of some metal salts with 1,1' bis – (ortho amino phenyl thio) – methane , J.Al-Mustansiriya Sci.19(12):59- 62 . 7. Naji,S.H.(2008)synthesis and spectral studies of transition metals (CoII,NiII,CuII,CdII,HgII,PbII) with aniline – 2 – thio methylene chloride complexes ,J.Al - Mustansiriya Sci.19(11):53-56 . 8. Naji , S.H. and Musa ,F. H. (2010)synthesis ,spectroscopic and Biological studies of some metal complexes with 1,2 bis – (ortho amino phenyl thio) ethane , J. Al – Mustansiriya Sci.21(3):35-50 . 9. Naji , S.H. ( 2011) Synthesis , Spectroscopic and biological studies of some metal complexes with ortho amino hydrazo benzene , J. Baghdad . Sci . 8(2):375-387 . 10. Manhel , R.A. ( 2010) synthesis of pheyl alanine Schiff Base ligand and its complexes with some metal (II) ions and Evalulation of their Anti bacterial Activity , J.Al – Mustansiriya Sci. 21(3):65 – 78 . 11. Bellamy , L.J. ( 1975)The infrared spectra of complex molecules , Hasted press , Division of John Willey and sons , Inc.,ed. 3rd . New York . 12. Cooper , J.W. ( 1980) spectroscopic Techniques for organic chemistry , John Willey and sons , ed. 2nd ., New York . 13. Keeton , M. N. ; and Lever . A.B.P. ( 1971) Four , Five ,and Six coordinate metalcomplexes of di(2 pyridyl ) disulphide and 1, 2 –di ( 2` – pyridyl ) ethane , Inorg. Chem. 10 (5):49 -52. 14. AL–Obadi , N. J.; Abid ,K. K. and AL–Naimi , Y. J. (2006) Transition metal complexes of 2 – (thiosemicarbazino ) – 5 – ( o – hydroxyl phenyl ) – 1 , 3 , 4 –oxadiazole , J. Tikrit . Sci. 11(24):164–167. 15. Saha , B. G. and Banerji , S. K. (1982) Synthesis and characterization of complexes , J. Indian Chem., Soc, 1(5): 928 – 932 . 16. Bahel , S.C. ( 1982) Synthesis and structural studies of complexes of Zn(II),Ni(II),and Co(II) with 3 –Aryloxymethyl 4 – aryl – 5 mercapto – 1 , 2 , 4 – triazoles , J. Indian .1(3):1127 – 1135 . 17. Iskender , M. F.; El –Sayed , L.; Hefny ,A. F. and Zayan . S. E. (1976) structural studies of some metal ions ; J. Inorg Chem, 38 (1):13 – 19 . 18. Greay ,W. G. (1970)Coordination Chemistry reviews , Elsevier publishing company , ed. 3rd ., Amsterdam . 19. Clark , R. J. H. and Erring ton . W. R. (1966)Sulpher donor complexes , Inorg . Chem., 5(2):650–660 . 20. Kadeoka , W. N. (1976) Crystal and Molecular structure of Dichloro bis ( 2 – pyridyl ) disulphide cobalt(II) , Inorg Chem. 15 (12):812 – 820 . 21. Foresman , J. C. J. and Frisch, C . A. ( 1996) Exploring chem , With Elecronic structure methods , Gaussian – Inc , ed. 2nd ., Pittsuburgh . 22. Rudolph , W. K. (1965) Mixed chelates from thio picolinamides and β – diketones , Inorg Chem. 4 (11):1047 – 1055 . 23. El – Asmy , A. A. ( 1990) Structural studies on Cd(II) , Co (II) , Cu (II) , Ni (II) and Zn (II) complexes of 1 – malonyl – bis ( 4-phenyl thio semicarbazide ) ,Transition Met. Chem. 4 (5): 12 24. Sutton , D.L. (1968) Electronic Spectra of Transition metal complexes , Mc Graw – Hill , ed.1st . , London . 198 | Chemistry @@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@Ü‹1a26@@ÖÜ»€a@I1@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (1) 2013 25. Gajendragad , M.R. and Agarwala. U.A. ( 1975) Synthesis and characterization of complexes , J. Inorg Nucl. Chem. 37(11):29 – 35 . 26. Figgis , B. N. ( 1966)Introduction to ligand Fields , John – Wiley and sons , Inc., ed. 2nd ., New York . 27. Figgis , B. N. and Lewis. J.N( 1967) Modern Coordination Chemistry,eddited by Lewis and Wilkins R. G. ; Interscience , ed. 3rd. , New York . 28. Dubey , S. N. and Kaushik . B. N.(1985) Triazoles copmplexing Agent , Indian J.Chem. 24(8):950-959. Table (1):Color , melting point , yield , metal analysis and solubility for the ligand(L) and its complexes Solubility Metal analysis found ( calculated ) Yield % m. p. co or (dec) Color no. of mole and gm compound No. M % N % H % C % ETOH , CCl4 , CH Cl3 ,C7H8, DMF,DMSO __ 21.230 (21.105) 6.531 (6.532) 72.29 (72.361) 85 83 yellow 1.00 0.19 (L) C12H13N3 1 DMF , DMSO 14.923 (14.545) 11.725 (11.748) 3.549 (3.636) 40.253 (40.279) 72 152 green 1.00 0.26 L-CrCl3 2 DMF , DMSO __ 12.110 (12.103) 4.213 (4.322) 41.508 (41.498) 63 204 (dec) Dark blue 1.00 0.24 L-CoCl2.H2O 3 DMF , DMSO __ 12.108 (12.114) 4.421 (4.326) 41.483 (41.534) 74 184 Light green 1.00 0.24 L-NiCl2.H2O 4 DMF , DMSO 18.678 (18.088) __ __ __ 81 174 blue 1.00 0.17 L-CuCl2.H2O 5 DMF , DMSO 28.023 (28.267) 11.098 (11.158) 3.395 (3.453) 38.241 (38.257) 92 210 (dec) Brown 1.00 0.17 L-PdCl2 6 DMF , DMSO 27.987 (28.071) ___ __ __ 88 202 (dec) Yellow 1.00 0.27 L-CdCl2.H2O 7 DMF , DMSO 42.012 (41.044) ___ __ __ 87 192 Violet 1.00 0.33 L-HgCl2.H2O 8 DMF , DMSO __ 12.751 (12.773) 2.715 (2.737) 26.301 (26.277) 78 222 Light yellow 1.00 0.33 L-Pb(NO3)2.H2O 9 dec. = Decomposition 199 | Chemistry @@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@Ü‹1a26@@ÖÜ»€a@I1@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. 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Vol. 26 (1) 2013 Table(2) : Characteristic stretching vibrational frequencies (cm-1) located in the FT-IR of the ligand(L) and its complexes NO3 cm -1 (M-O) ט .aq(OH2) ט cm -1 (M-X) ט cm -1 (M-N) ט cm -1 cm -1(C-H) ט Ali. cm -1(C-H) ט Ar. ט (N – H ) cm -1 compound No. __ ___ ___ ___ 2930(asym)(w) 2877(sym)(m) 1469(s),1442(s) 3186(m) 3066(m) 3380(asym)(m) 3298(sym)(m) 1612(s),1585(m) 1303(s),1246(s) (L) C12H13N3 1 __ ___ 410(s) 528(s) 2930(br) 2823(m) 1473(s),1435(s) 3190(m) 3074(m) 3414(asym)(br) 3356(sym)(br) 1608(s),1546(s) 1315(s),1234(m) L-CrCl3 2 __ 551(s) 830(s) 412(s) 515(s) 2920(m) 2880(m) 1477(s),1442(s) 3190(w) 3066(m) 3414(asym)(br) 3340(sym)(br) 1604(s),1573(m) 1303(s),1249(s) L-CoCl2.H2O 3 __ 550(s) 829(s) 412(s) 520(s) 2924(m) 2850(m) 1473(s),1442(s) 3120(s) 3082(s) 3062(s) 3410(asym)(br) 3282(sym)(s) 1612(sh), 1593(s) 1315(m),1226(s) L-NiCl2.H2O 4 __ 551(s) 817(s) 416(s) 536(s) 2940(m) 2890(w) 1492(s),1427(s) 3190(w) 3086(m) 3452(asym)(br) 3352(sym)(br) 1600(s),1558(w) 1307(s),1253(s) L-CuCl2.H2O 5 ___ ___ 415(s) 515(s) 2935(w) 2885(w) 1473(s),1442(s) 3182(br) 3055(br) 3414(asym)(br) 3390(sym)(br) 1604(br),1558(br) 1307(m),1265(br) L-PdCl2 6 ___ 545(m) 817(m) 408(s) 513(s) 2927(m) 2890(m) 3180(m) 3062(s) 3379(asym)(m) 3305(sym)(m) 1608(s),1562(sh) 1307(s),1246(s) L-CdCl2.H2O 7 ___ 563(m) 825(m) 410(s) 520(s) 2990(w) 2893(br) 1442(w),1473(m) ,1492(m) 3190(m) 3059(m) 3417(asym)(br) 3317(sym)(br) 1604(s),1570(sh) 1319(s),1249(s) L-HgCl2.H2O 8 933(s) 663(s) 540(m) 837(m) 405(s) 516(s) 2966(m) 2876(m) 1473(s),1442(s) 3186(m) 3066(m) 3460(asym)(s) 3371,3302(sym)(s) 1608(s),1566(s) 1307(s),1246(s) L-Pb(NO3)2.H2O 9 200 | Chemistry @@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@Ü‹1a26@@ÖÜ»€a@I1@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. 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Vol. 26 (1) 2013 Table (3) : Electronic spectra DMSO, conductance in DMSO magnetic moment (B.M) of the ligand (L) and its complexes. µ eff (B.M) Λ s. cm -1 DMSO (10- 3M) Assignment Bands ג (nm) Cm -1 compound No. ___ ____ π – π * n – π 37453(267) 31948(313) 28328(353) (L) C12H13N3 1 3.77 20.30 4A2g4T2g 17241(580) L-CrCl3 2 4.82 9.34 4T1g4T2g(F) 4T1g4A2g 4T1g2Eg 19230(520) 15151(660) 12500(800) L-CoCl2.H2O 3 3.01 11.23 3A2g  3T1g 12121(825) L-NiCl2.H2O 4 1.98 18.80 2Eg 2T2g 15151(660) L-CuCl2.H2O 5 ___ 8.20 1A1g  1B1g 25000(400) L-PdCl2 6 ___ 6.15 Charge- transfer 27173(368) L-CdCl2.H2O 7 ___ 9.26 Charge-transfer 32258(310) L-HgCl2.H2O 8 ___ 9.23 Charge-Transfer 28571(350) L-Pb(NO3)2.H2O 9 B.M = Bohr Magneton Table (4):continuous variation slop for Cr+3ion λ(368mm) L – Cr Cl3 V M VL Abs 1 ml 1 1 1 1 1 1 1 1 1 0.25 0.50 0.75 1 1.25 1.50 1.75 2 2.25 2.5 0.15 0.21 0.43 0.60 0.58 0.61 0.61 0.62 0.63 0.61 Table (5):continuous variation slop for Co+2ionλ(350mm) L – CoCl2.H2O V M VL Abs 1 ml 1 1 1 1 1 1 1 1 1 0.25 0.50 0.75 1 1.25 1.50 1.75 2 2.25 2.5 0.41 0.74 1.11 1.50 1.48 1.51 1.49 1.46 1.52 1.51 Table (6):continuous variation slop for Ni+2ion λ(348mm) L – NiCl2.H2O V M VL Abs 1 ml 1 1 1 1 1 1 1 1 1 0.25 0.50 0.75 1 1.25 1.50 1.75 2 2.25 2.5 0.22 0.44 0.68 0.90 0.89 0.91 0.92 0.93 0.91 0.91 Table (7):continuous variation slop for Cu+2ionλ(336mm) L – Cu Cl2.H2O V M VL Abs 1 ml 1 1 1 1 1 1 1 1 1 0.25 0.50 0.75 1 1.25 1.50 1.75 2 2.25 2.5 0.21 0.41 0.62 0.80 0.81 0.79 0.78 0.82 0.83 0.79 201 | Chemistry @@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@Ü‹1a26@@ÖÜ»€a@I1@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. 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Vol. 26 (1) 2013 Table(8) : As,Am,Kf,Єmax and λmax of the Cr+3,Co+2,Ni+2,Cu+2 complexes Maxג (nm) Molar Absorpitivity εmax L.mol-1.cm-1 Formation Constant (Kf) α Am As Compound NO. 368 2983 4.314x 105 0.043 0.63 0.60 Cr-complex 1 350 4702 5.840x106 0.013 1.52 1.50 Co-complex 2 348 1048 9.462x105 0.051 0.93 0.90 Ni-complex 3 336 2105 7.378x105 0.0361 0.83 0.80 Cu-complex 4 Table(9): Effect of the ligand and its complexes on gram positive and gram negative bacteria Diameter of inhibition zone (mm) at concentration 5mg/ml Diameter of inhibition zone (mm) at concentration 1mg/ml Diameter of inhibition zone (mm) at concentration 5mg/ml Diameter of inhibition zone (mm) at concentration 1mg/ml compound No. E.coli Staphylococcus aureus 35 80 50 40 (L) C12H13N3 1 15 10 32 30 L-CrCl3 2 26 25 20 18 L-CoCl2.H2O 3 40 30 24 14 L-CuCl2.H2O 4 25 22 40 30 L-PdCl2 5 20 18 26 22 L-HgCl2.H2O 6 202 | Chemistry @@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@Ü‹1a26@@ÖÜ»€a@I1@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (1) 2013 Fig. (3): Infrared spectrum of the lignd (L). 203 | Chemistry @@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@Ü‹1a26@@ÖÜ»€a@I1@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (1) 2013 Fig. (4): Infrared spectrum of L-NiCl2.H2O . Fig. (5): UV-visible spectrum of the ligand (L). 204 | Chemistry @@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@Ü‹1a26@@ÖÜ»€a@I1@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (1) 2013 Fig. (6): Tanabe-Sugano diagram of the Co+2 ion in Octahedral complexes. Fig. (7): UV-visible spectrum of L-NiCl2.H2O . 205 | Chemistry @@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@Ü‹1a26@@ÖÜ»€a@I1@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (1) 2013 Fig.(8):The molar-ratio curve Fig.(9):The molar ratio curve The complex L-CrCl3 The complex L- CoCl2.H2O Fig.(10):The molar-ratio curve Fig.(11):The molar-ratio curve the complex L-NiCl2.H2O the complex L-CuCl2.H2O 0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2 0 0.25 0.5 0.75 1 1.25 1.5 1.75 2 2.25 2.5 2.75 3 A bs or ba nc e L / M 0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2 0 0.25 0.5 0.75 1 1.25 1.5 1.75 2 2.25 2.5 2.75 3A bs or ba nc e L / M 0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2 0 0.25 0.5 0.75 1 1.25 1.5 1.75 2 2.25 2.5 2.75 3A bs or ba nc e L / M 0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2 0 0.25 0.5 0.75 1 1.25 1.5 1.75 2 2.25 2.5 2.75 3A bs or ba nc e L / M 206 | Chemistry @@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@Ü‹1a26@@ÖÜ»€a@I1@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (1) 2013 دراسة طیفیة وبایولوجیة لبعض المعقدات الفلزیة الجدیدة مع وتحضیر N – ثنائي امین -1,2-بنزین –یل مثیل -2-بریدین شیماء ھادي ناجي لقاء خالد عبدالكریم فالح حسن موسى / كلیة التربیة للعلوم الصرفة (ابن الھیثم) / جامعة بغدادالكیمیاء علوم قسم 2012شباط 12قبل البحث في: ، 2011تشرین الثاني 23استلم البحث في : الخالصة ثنائي امین من تفاعل اورثو أمینو فنیل ثایول مع -1,2-بنزین –یل مثیل -2-بریدین – L (Nحضر اللیكاند الجدید( ) األشعة تحت الحمراء ، األشعة N.H.Cوشخص بوساطة التحلیل الدقیق للعناصر ( 1:1أمینو مثیل بریدین وبنسبة - 2 المرئیة وطیف الرنین النووي المغناطیسي كما حضرت وشخصت معقدات أمالح بعض ایونات العناصر –فوق البنفسجیة ). استعملت تقنیات L) مع اللیكاند (Crاالیون الثالثي التكافؤ ( ) و ,Pd , Cu , Ni ,Co Pb,Hg,Cdالثنائیة التكافؤ ( المرئیة و التوصیلیة الكھربائیة و االمتصاصیة -) ، األشعة تحت الحمراء واألشعھ فوق البنفسجیةN.H.Cتحلیل العناصر ( ) Lایون الفلز مع اللیكاند (الذریة والحساسیة المغناطیسیة وأستنتج من التحالیل ان المعقدات لھا شكل ثماني السطوح حول لمعقد βللمعقدات وحساب max,Kf, α Єمعطیاً الشكل مربع مستو وقد حسبت قیم Pd) ماعدا N,N,Nثالثي السن ( الكوبلت . كما درست الفعالیة البایولوجیة للیكاند ومعقداتھ وقد اظھرت النتائج امتالكھا فعالیة متفاوتھ اتجاه انواع البكتریا E.coli , Staphylococcus aureus . تحلیل ، فنیل ثایول ،معقدات ، دراسة بایولوجیة ،ایونات ثنائیة التكافؤ الكلمات المفتاحیة : 207 | Chemistry