IBN AL- HAITHAM J. FO R PURE & APPL. SC I VO L.22 (3) 2009 Complexeation Behavior of CoII, NiII, CuII, ZnII, and CdII Ions Toward Schiff Base Derived From 2, 4 -Dihydroxy Benzaldehyde and O-Phenylene Diamine A. .T. Numan, K. .M. Sultan and A.S. Abdullah Department of Chemistry, College of Education, Ibn Al-Haitham, University of Baghdad, P.O. 4150, Adhamiyah, Baaghdad, Iraq. Abstract The aim of this work covers the synthesis and characterization of the new tertra dentate ligand (H4L) containing (N and O) as donor set atoms kind (N2O2) where: H4L=Bis-1,2 (2,4- dihydroxybenzylediene phylinediamine . The preparation of ligand contains reaction 2, 4 - Dihydroxy benzaldehyde and o-phenylene diamine . Schiff base was reacted with some metal ions in the presence of methanol to give the complexes in the general formula [M (H2L)] where: MII = Co, Ni, Cu, Zn, Cd. All compounds were characterized by spectroscopic methods I.R , U.V.-Vis, metal content and molar conductivity measurements, showed that the complexes are non-electrolyte. The proposed geometry for all of the proposed complexes was a tetrahedral while Ni complex was square planar. Introduction Metal complexes of Schiff base are extensively studied due to synthetic flexibility and sensitivity toward a variety of metal atoms (1). They are found useful in catalysis, in medicine as antibiotics and anti-inflammatory agent and in the industry as anti-corrosion (2-8). salicylaldehyde compound is a bidentate ligand and has several applications in chemistry and medicine .In 2005 Halabiand and co-workers (9) prepared a Schiff base ligand (N2O2) kind derived from amino -1,2,3,6-oxatrizain and salicylaldehyde and its transition metal complexes with (Ni II, CuII ,and PdII). In this paper the synthesis and characterization of Schiff base [Bis-1,2 (2,4-dihydroxybenzylediene phylinediamine] ligand derived from the reaction of 2,4 -Dihydroxy benzaldehyde and o-phenylene diamine ,and some of its complexes with (Co, Ni, Cu, Zn and Cd) are reported. Experimental Reagents were purchased from Fluka and Redial-Dehenge chemical Co. I.R spectra were recorded as (KBr) dicsic a shimadzu 8300 FTIR Spectrophotometer in the range (4000-400) cm -1 . Electronic spectra of prepared compounds were measured in the region (200-1100) nm for 10 -3M solutions in (DM F) as a solvent at 25 C˚ by using a shimadz, 160 spectrophotometer with 1.000 + 0.001cm-1 matched quartz cell. While metal contents of the complexes were determined by atomic absorption (A.A) technique using a shimadz AA .680G atomic absorption spectrophotometer .Electrical conductivity measurements of the complexes were recorded at 25 C˚ for 10 -3 M solutions of the samples in (DM F)by using a PW 9526 digital conductivity meter . Synthesis of the ligand (H4L) A solution of (o-phenylene diamine), (0.59g, 4.6 mmole) in methanol (5ml) was added slowly to 2,4-Dihydroxy benzaldehyde ( 1.27 g, 9.2 mmole) dissolved in methanol (5ml) . Then added drops from glacial acetic acid to them. The mixture was refluxed for (4hrs) and then stirred IBN AL- HAITHAM J. FO R PURE & APPL. SC I VO L.22 (3) 2009 at room temperature for (1 hr). A pale yellow precipitate was collected by filtration, dried under vacuum for (24 hr), to give (H4L), Yield (84%), m.p. (198) dec. Synthesis of [(Co (H2L)] complex A (0.226g, 0.82 mmole) of CoCl2.6H2O was dissolved in (5 ml) methanol. A solution of (0.2g, 0.95 mmole) of the ligand (H4L) in (15 ml) methanol was added to the above mixture, then (0.106 g, 0.89 m mole) of KOH was dissolved in methanol and added to them. The reaction was allowed to reflux for (3 hrs), a dark violet the precipitate which were collected ,and washed with (2ml) benzene ,then let it to dry to give (0.25g), yield (80%), mp (280 0 C) dec. The method that was used to prepare the other complexes [Ni (H2L)] (2), [Cu (H2L)] (3), [Zn (H2L)] (4) and [Cd (H2L)](5) was similar to that mentioned in the preparation of [Co (H2L)] complex. Table (1) Shows some physical properties of the prepared complexes: Results and Discussion The new ligand type (N2O2) was prepared according to the general method shown in Scheme (1). Bis-1,2 (2,4-dihydroxybenzylediene phylinediamine Scheme (1) Synthesis route of the Schiff base The (1.R) spectrum for (H4L) ligand Fig (1) displayed two bands at (1610) and (1587) cm-1 due to the υ (C=N) stretching for the imine groups respectively (10) .The band at (3355) cm -1 is attributed to υ (O-H) stretching, the strong bands at (1342) and (1217) cm -1 are attributed to υ (C- N) and υ (C-O) stretching respectively. The (I.R) spectral data of the complexes are presented in Table (2) .In general the (I.R) spectra of the complexes show two bands at the range (1600-1541) cm-1 which assigned to the υ NH2H2N 1 mole + C O H HO OH 2 mole methanol reflux glacial acetic acid NN CHHC OH HO HO OH IBN AL- HAITHAM J. FO R PURE & APPL. SC I VO L.22 (3) 2009 (C=N) stretches frequency for the imine groups which are shifted to alower frequency by (10-46) cm -1 in comparison to that for the free ligand fig (1a, 1b and 1c), these shiftings could be attributed to the reduced bond order of the imine group . This can be attributed to delocalization of metal electrons density at (t2g) in the π system of the ligand (HOM O → LUM O)(12-14). Where: HOMO = highest occupied molecular orbital. LUMO = lowest unoccupied molecular orbital. The υ (O-H) stretching band in the free ligand at (3355) cm -1 is still present at the (3550- 3450) cm -1 range for these complexes (15). The new bands at the range (447-541) cm- 1were assigned to υ (M-O) and υ (M-N) stretching respectively, indicating that the imine nitrogen and oxygen of hydroxyl group were involved in coordination with metal ion Table(2) (16-22). (U.V-Vis) spectrum for the ligand Fig (2) exhibits a high intense absorption peak at (301) nm (33222cm-1) εmax = 417 molar -1.cm-1 which is assigned to overlap of (π → π*) and (→ *) transitions (11) Table (3).The reaction of (H4L) ligand with [MCl2.H2O] (where M=Co, Ni, Cu, Zn, and Cd) was carried out in MeOH under reflux.. The analytical and physical data Table (1) and spectral data Table (2) and Table (3). The electronic spectral data of the complexes are summarized in Table (3) .The (U.V-Vis) spectra of the complexes displayed absorption at the range (314-342) nm which were assigned to the ligand filed (23). In the [Co (H2L)] complex the band at (430) nm was attributed to (d-d) electronic transition type (4 T1(p)← 4 A2) (24), suggesting tetrahedral structure about Co ion. The band at (455) nm in the spectrum of [Ni (H2L)] complex was attributed to (d-d) electronic transition type (1B1g←1A1g) (Fig-2a), suggesting a square planar structure about Ni ion (25-27), (Fig-2b), while the band at (449) nm in the spectrum of [Cu (H2L)] complex which was assigned to (d-d) electronic transition type ( 2E←2B2), suggesting tetrahedral structure about Cu ion. The absence of (d-d) electronic transition in the complexes [Zn (H2L)] and [Cd (H2L)] are due to the configuration (d10) structure for the metal ions, suggesting tetrahedral structure for sp 3 hyperdization of (Zn and Cd) (28). The molar conductance values determined in (DM F) solution (10 -3 M) (Table-3) lie in the range (23.5-3.19 s.cm-1 mole -1 ) indicates that the complexes are non electrolytes (23) and confirm the suggested formula [M (H2L)] The experimental data of metal content is obtained by the atomic absorption method and the chloride content for all of the prepared complexes, Table (1) are in a good agreement with the calculated values. References 179.:47Acta Chime. Slov., )2000. (A ,and Kriza .C,Spinu -1 1043.:(11)12Chin.Chem.Lett., .J)2001.(X ,and Li .Y .Hu ,J .;J ,Chen.;B ,Sun-2 5356. :(26)58Tetrahedron )2002. (S , and Mohebi .M .D ,Boghaei-3 41.:30Turk J.Chem., )2006. (Y ,and Liu .B ,Zhang.; B ,Wu. ;J ,Liu-4 5-Britovsek, G .J. P. ;Gibson, V. V.; Mastroianni, S.;Oakes, D. C. H.; Redshaw, C.; Solan ,G .A.; 431:(2)2001Eur.J.Inorg.Chem ., )2001. (J .D ,and Williams .P .J.A ,White 63.:(1)41 Med.Chem. J. )2006( .A,and Azam .M ,Abid.; A ,Budakoti-6 677 :(3)358Inorg. Chim.Acta., )2005. (D. J ,and Ranford .I .S ,Tan.; X .V ,Jin-7 1:(319)13Int.Corros.Cong. Proc., )1996( .S .V , and Agarwala .K .N ,Mehta-8 IBN AL- HAITHAM J. FO R PURE & APPL. SC I VO L.22 (3) 2009 9-EI-Halabi,M.N.and Awadallah, M. (2005),Journal of the Isalmic university of Gaza,(series of 90.-85 :)2(13natural studies and Engineering) 10- Socrates,G. (1980) Infrared Characteristic Group Frequencies, Wiley-Interscienc Publication. 11- Kemp,W. (1987)Organic Spectroscopy, 2 nd .Edition, :144. 12- Hadzi ,D. and Premru ,L. (1967)Spectrochim.Acta.23A, 35. 13- Pinchas ,S. and Benishai, D. (1998). J.Amer Chem.72, 519, 14- Clara, Sousa, Cristina Freire and Baltazar decastro , ,, synthesis and characterization of Benzo- 895-894 :8Molecules (2003) ,,O Schiff Bases2Ether with Appended N -5-15crown 193:26Spectrochim .Acta, , )1970( G. Dealti, V. and ,Galasso ;G. Costa,;A. Bigatto, -15 16- Nakamoto, K. (1996)Infrared Spectra of Inorganic and Coordination Compounds, 4th .ED.,J.Wiely and Sons ,New York, 17- Ferraro,J. (1971).Low Frequency Vibrations of Inorganic and Coordination Compounds ,, Plenum, New York, 18- Nanjappan, P.; Ramalingam ,K.; Jurisson ,S.; Pirro, J. ;Diroxo, R.; Narra, R.K.; Nowotinik D.P. and Nunn,A.D. (1992)Abstracts of papers, Ninth International Symposium on Radiopharmaceutical Chem, Paris 6-10 April. 19- Raju ,K.C. and Radhakrishnan ,P.K. (2003).Complexes of Copper with 2,3 Dimethy -4- formyl (benzhydrazide) -1- phenyl -3- pyrazolin -5- one synthesis and reactivity in inorganic 1318-1307 ):8(33and metal ,organic chemistry , 519 :72polish.J.chem. (1998) T.I.Kasher,A.S. and ,Tble -EL -20 21- EL-Sonbati ,A.Z. and Bindary,A.A. (2000). Stereochemistry of New Nitrogen Containing Aldehades .V.Novel Synthesis and Spectroscopic studies of some quinoline Schiff Bases 630 -621 :74polish J.chem: complexes, 81.:7Coord.Rev, )1971(W.J. Geary, -22 23- Greenwood ,N.N. and Earnshow, A. (1998) Chemistry of the Elements ,2nd eddtion.Wiley and Sons Inc. New York, 24- Lever,A.B.P. (1968).Inorganic Electronic Spectroscopy, New York, 660 :15Inorg .chem. )1916( S.C. ,Cummings M.S. and,Holtman -52 26- Skopenko,V.V.; Fristskii, I.O.; lempleka, R.D. and Iskenderov,T.S. (1993) 1827.: 38Russ.J.Inorg.Chem., 97.:1 Accounts Chem.Res.)1968(G.N. Schrauzer, -72 849 :2J.R., Inorg.Chem. (1963) S.L.Holt,R.L. and ,Carlin -82 IBN AL- HAITHAM J. FO R PURE & APPL. SC I VO L.22 (3) 2009 Table (1) Some physical properties of the complexes and their reactants quantities. dec: decomposition Table (2): I.R spectral data of the ligand and its complexes (cmˉ¹) Compound decomposition temperature 0C Color Weight of metal Weight of product g Yield % M.Wt g.mol -1 Chloride content Metal Content g mmole Found (calc) (H4L) 198 dec pale yellow - - 1.02 80 210.12 Nil - [(Co(H2L) ] 280 dec dark violet 0.2.0 0.82 0.25 80 266 Nil 14.06 (13.63) [Ni(H2L)] 270 dec red 0.226 0.82 0.28 67 266 Nil 14.46 (13.33) [Cu(H2L)] 210 dec brown 0.16 0.84 0,2 66 271 Nil 15.01 (14.67) [Zn(H2L)] 200 dec Yellow 0.129 0.82 0.25 81 273 Nil 16.54 (15.85) [Cd(H2L)] 255 dec Yellow 0.2 0.86 0.42 92 322 Nil 24.21 (22.54) Additional peaks υ (M-O) υ (M-N) υ (C-O) υ (C-N) υ (C-H) υ (N=C) υ (O-H) Formula No. - - - 1217 1342 3060 2752 1610 1587 3355 [H4L] 1 1438(C=C) ring 447 503 1265 1373 - 1600 1541 3550 [Co(H2L)] 2 1448(C=C) ring 507 541 1242 1371 3078 2921 1602 1552 3527 [Ni(H2L)] 3 1477(C=C) ring 495 532 1236 1369 3178 3066 1602 1554 3539 [Cu(H2L)] 4 1541(C=C) ring 487 524 1240 1355 3209 3072 1604 1558 3450 [Zn(H2L)] 5 1446(C=C) ring 482 526 1276 1350 2786 1606 1558 ----- [Cd(H2L)] 6 IBN AL- HAITHAM J. FO R PURE & APPL. SC I VO L.22 (3) 2009 Table (3): Electronic spectral data and conductance measurement in DMF as asolvant Assignment Λm s.cm2.mole-1 ε max molar-1 cm-1 nm λ Compound π→π * n→π* - 1121 301 (H4L) 4T1(p)← 4A2(f) 23.5 403 505 342 430 [Co(H2L)] 1B1g←1A1g 3.19 414 448 342 455 [Ni(H2L)] 2 E← 2 B2 3.65 547 3952 314 449 [Cu(H2L)] C.T 4.33 423 321 [Zn(H2L)] C.T 5.40 414 341 [Cd(H2L)] Fig. (1): The (I.R) Spectrum of the ligand Fig. (1a): The(I.R) Spectrum of [(Ni (H2L)] complex IBN AL- HAITHAM J. FO R PURE & APPL. SC I VO L.22 (3) 2009 Fig. (1b):The(I.R) Spectrum of [(Cu (H2L)] complex Fig. (1c): The(I.R) Spectrum of [Cd(H2L)] complex Fig(2) The (UV-Vis)Spectrum of The ligand (H2L)] complex IBN AL- HAITHAM J. FO R PURE & APPL. SC I VO L.22 (3) 2009 Fig. (2a): The (UV-Vis) Spectrum of complex [(Ni (H2L)] Fig. (2b): The (UV-Vis) S pectrum of complex [(Cu (H2L)] IBN AL- HAITHAM J. FO R PURE & APPL. SC I VO L.22 (3) 2009 NN C HH C O O H O H O M f ig u r e ( 3 ) th e s u g g e st e d s t r u c tu r e f o r th e M ( H 2 L ) c o m p le x e s M = C o , Z n ,C d NN C HH C O O H O H O N i f ig u r e ( 4 ) th e su g g e s te d s t r u c tu r e o f t h e N i ( H 2L ) c o m p le x 2009) 3( 22مجلة ابن الھیثم للعلوم الصرفة والتطبیقیة المجلد و الزنك ،والنحاس الثنائي ،والنیكل الثنائي،سلوك التخلب االیوني للكوبلت الثنائي والكادمیوم الثنائي اتجاه قاعدة شیف المشتقة من اورثو فنیلین داي امین ،الثنائي داي هایدروكسي بنزلدیهاید -4,2و سلطان،اواز صالح الدین خولة محمد،أحمد ثابت نعمان د ،كلیة التربیة ابن الهیثمقسم الكیمیاء ، جامعة بغدا الخالصة N2O2 الجدید الرباعي السن نوعتضمن البحث تحضیر اللیكند Bis-1,2-(2,4-dihydroxybenzylediene phylinediamine =(H4L) وذلك من مفاعلة بعض ایونات العناصر مفاعلة اللیكند مع ثم 2,4- Dihydroxy benzaldehyd مع) (o-phenylene diamine) )Co ll , Ni ll ,Cu ll , Zn ll , Cd ll تكونت اذ ،المیثانول وسطا للتفاعل وبوجود هیدروكسید البوتاسیوم قاعدة المعباست) . [M(H2L)]الصیغة العامة يسلسلة من المعقدات ذ ،مطیافیة المرئیة –األشعة تحت الحمراء ، واألشعة فوق البنفسجیة ، ق الطیفیةائجمیع المركبات بالطر شخصت .مع قیاس التوصیلیة الموالریة الكهربائیة، محتوى الكلور ودرجات االنصهارین وعاالمتصاص الذري للعناصر بینما ،السطوح مشوه هي رباعي والزنك والكادمیوم من نتائج البحث كان الشكل الفراغي المقترح لمعقدات الكوبلت والنحاس .نیكل فكان شكل معقده مربعا مستویالل