IBN AL- HAITHAM J. FO R PURE & APPL. SC I VO L.22 (3) 2009 Complexeation Behavior o f 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 Departme nt of Chemistry, College of Education, I bn Al-Haitham, Unive rsity of Baghdad, P.O. 4150, Adhamiyah, Baaghdad, I raq. Abstract The aim of this work covers the sy nthesis 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- dihydroxy benzy lediene p hy linediamine . The p reparation of ligand contains reaction 2, 4 - Dihy droxy benzaldehy de and o-p henylene diamine . Schiff base was reacted with some metal ions in the p resence of methanol to give the complexes in the general formula [M (H2L)] where: M II = Co, Ni, Cu, Zn, Cd. All comp ounds were characterized by sp ectroscop ic methods I.R , U.V.-Vis, metal content and molar conductivity measurements, showed that the comp lexes are non-electrolyte. The p rop osed geometry for all of the p rop osed comp lexes was a tetrahedral while Ni complex was square p lanar. Introduction M etal comp lexes of Schiff base are extensively st udied due to sy nthetic 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 indust ry as anti-corrosion (2-8). salicylaldehy de comp ound is a bidentate ligand and has several app lications in chemist ry and medicine .In 2005 Halabiand and co-workers (9) p repared a Schiff base ligand (N2O2) kind derived from amino -1,2,3,6-oxatrizain and salicylaldehy de and its transition metal comp lexes with (Ni II , Cu II ,and Pd II ). In this p aper the sy nthesis and characterization of Schiff base [Bis-1,2 (2,4-dihydroxy benzy lediene phy linediamine] ligand derived from the reaction of 2,4 -Dihy droxy benzaldehy de and o-p henylene diamine ,and some of its comp lexes with (Co, Ni, Cu, Zn and Cd) are reported. Experime ntal Reagents were p urchased from Fluka and Redial-Dehenge chemical Co. I.R sp ectra were recorded as (KBr) dicsic a shimadzu 8300 FTIR Sp ectrop hotometer in the range (4000-400) cm -1 . Electronic sp ectra of p repared comp ounds were measured in the region (200-1100) nm for 10 -3 M solutions in (DM F) as a solvent at 25 C˚ by using a shimadz, 160 sp ectrop hotometer with 1.000 + 0.001cm -1 matched quartz cell. While metal contents of the comp lexes were determined by atomic absorp tion (A.A) technique using a shimadz AA .680G atomic absorp tion sp ectrop hotometer .Electrical conductivity measurements of the comp lexes were recorded at 25 C˚ for 10 -3 M solutions of the samp les in (DM F)by using a PW 9526 digital conductivity meter . S ynthesi s of the ligand (H4L) A solution of (o-p henylene diamine), (0.59 g, 4.6 mmole) in methanol (5ml) was added slowly to 2,4-Dihy droxy benzaldehy de ( 1.27 g, 9.2 mmole) dissolved in methanol (5ml) . Then added drop s from glacial acetic acid to them. The mixture was reflu xed for (4hrs) and then st irred IBN AL- HAITHAM J. FO R PURE & APPL. SC I VO L.22 (3) 2009 at room temp erature for (1 hr). A p ale yellow p recipitate was collected by filtration, dried under vacuum for (24 hr), to give (H4L), Yield (84%), m.p. (198) dec. S ynthesis of [(Co (H2L)] complex A (0.226g, 0.82 mmo le) of CoC l2.6H2O was dissolved in (5 ml) methanol. A solution of (0.2g, 0.95 mmole) of the ligand (H4L) in (15 ml) methanol was add ed to t he above mi xture, then (0.106 g, 0.89 m mole) of KOH was dissolved in methanol and added to them. The reaction was allowed to r eflu x for (3 hrs), a dark vio let the precipitate which were collected ,and washed with (2ml) benzene ,then let it to dry to give (0.25 g), y ield (80%), mp (280 0 C) dec. The method that was used to p rep are the other comp lexes [Ni (H2L)] (2), [Cu (H2L)] (3), [Zn (H2L)] (4) and [Cd (H2L)](5) was similar to that mentioned in the p rep aration of [Co (H2L)] comp lex. Table (1) Shows some phy sical prop erties of the p rep ared comp lexes: Results and Discussion The new ligand typ e (N2O2) was p repared accordin g to the gener al method shown in Scheme (1). Bis-1,2 (2,4-dihydroxybenz ylediene phylinediamine S cheme (1) S ynthesis route of the S chi ff base The (1.R) sp ectrum for (H4L) ligand Fig (1) disp lay ed two bands at (1610) and (1587) cm -1 due to the υ (C=N) st retching for the imine group s resp ectively (10) .The band at (3355) cm -1 is att ributed to υ (O-H) st retching, the strong bands at (1342) and (1217) cm -1 are att ributed to υ (C- N) and υ (C-O) stretching resp ectively. The (I.R) sp ectral data of the comp lexes are p resented in Table (2) .In general the (I.R) sp ectra of the comp lexes show two bands at the range (1600-1541) cm -1 which assigned to t he 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) st retches frequency for the imine group s which are shifted to alower frequency by (10-46) cm -1 in comp arison to that for the free ligand fig (1a, 1b and 1c), these shiftings could be att ributed to the reduced bond order of the imine group . This can be attributed to delocalization of metal electrons density at (t 2g) in the π sy st em of the ligand (HOM O → LUM O)(12-14). Where: HOM O = highest occup ied molecular orbital. LUMO = lowest unoccup ied molecular orbital. The υ (O-H) stretching band in the free ligand at (3355) cm -1 is st ill p resent at the (3550- 3450) cm -1 range for these comp lexes (15). The new bands at the range (447-541) cm- 1 were assi gned to υ (M -O) and υ (M -N) st retching resp ectively, indicating that the imine nitrogen and o xy gen of hy droxy l group were involv ed in coordin ation with metal ion Table(2) (16-22). (U.V-Vis) sp ectrum for the ligand Fig (2) exhibits a high intense absorp tion p eak 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 [M Cl2.H2O] (where M =Co, Ni, Cu, Zn, and Cd) was carried out in M eOH under reflux.. The analytical and p hy sical data Table (1) and sp ectral data Table (2) and Table (3). The electronic sp ectral data of the complexes are summarized in Table (3) .The (U.V-Vis) sp ectra of the complexes disp lay ed absorpt ion at the range (314-342) nm which were assigned to the ligand filed (23). In the [Co (H2L)] comp lex the band at (430) nm was att ributed to (d-d) electronic transition ty p e ( 4 T1(p)← 4 A2) (24), suggesting tetrahedral structure about Co ion. The band at (455) nm in the sp ectrum of [Ni (H2L)] comp lex was att ributed to (d-d) electronic transition ty p e ( 1 B1g← 1 A1g) (Fig-2a), suggesting a square p lanar st ructure about Ni ion (25-27), (Fig-2b), while the band at (449) nm in the sp ectrum of [Cu (H2L)] comp lex which was assigned to (d-d) electronic transition ty p e ( 2 E← 2 B2), suggesting tetrahedral st ructure about Cu ion. The absence of (d-d) electronic transition in the complexes [Zn (H2L)] and [Cd (H2L)] are due to t he configuration (d 10 ) st ructure for the metal ions, suggesting tetrahedral structure for sp 3 hyp erdization 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 t he comp lexes are non electrolytes (23) and confirm the suggested formula [M (H2L)] The exp erimental d ata of metal content is obtained by the atomic absorpt ion method and the chloride content for all of the prepared comp lexes, Table (1) are in a good agreement with t he calcu lated values. Re ferences 179.:47Acta Chime. Slov., )2000. (A ,and Kriza .C,Sp inu -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 M ohebi .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.; M astroianni, 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 M ed.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 ,M ehta-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 Engineer ing) 10- Socrates,G. (1980) Infrared Characterist ic Group Frequencies, Wiley -Interscienc Publication. 11- Kemp,W. (1987)Organic Sp ectroscopy , 2 nd .Edition, :144. 12- Hadzi ,D. and Premru ,L. (1967)Sp ectrochim.Acta.23A, 35. 13- Pinchas ,S. and B enishai, D. (1998). J.Amer Chem.72, 519, 14- Clara, Sousa, Cristina Freire and Baltazar decastro , ,, sy nthesis and characterization of Benzo- 895-894 :8M olecules (2003) ,, O Schiff Bases2Ether with App ended N -5-15crown 193:26Sp ectrochim .Acta, , )1970( G. Dealti, V. and ,Galasso ;G. Costa,;A. Bigatto, -15 16- Nakamoto, K. (1996)Infrared Sp ectra of Inorganic and Coordination Compounds , 4 th .ED.,J.Wiely and Sons ,New York, 17- Ferraro,J. (1971).Low Frequency Vibrations of Inorganic and Coordination Compounds ,, Plenum, New York, 18- Nanjap p an, P.; Ramalin gam ,K.; Jurisson ,S. ; Pirro, J. ;Diroxo, R.; Narra, R.K.; Nowotinik D.P. and Nunn,A.D. (1992)Abstracts of p ap ers, Ninth International Sy mposium on Radiop harmaceutical Chem, Paris 6-10 Ap ril. 19- Raju ,K.C. and Radhakr ishnan ,P.K. (2003).Comp lexes of Cop p er with 2,3 Dimethy -4- formyl (benzhy drazide) -1- pheny l -3- py razolin -5- one sy nthesis and reactivity in inorganic 1318-1307 ):8(33and metal ,organic chemistry , 519 :72p olish.J.chem. (1998) T.I.Kasher,A.S. and ,Tble -EL -20 21- EL-Sonb ati ,A.Z . and Bindary,A.A. (2000). Stereochemist ry of New Nitrogen Containing Aldehades .V.Nove l Sy nthesis and Sp ectroscop ic studies of some quinoline Schiff Bases 630 -621 :74p olish J.chem: comp lexes, 81.:7Coord.Rev, )1971(W.J. Geary, -22 23- Greenwood ,N.N. and Earnshow, A. (1998) Chemistry of the Elements , 2 nd eddtion.Wiley and Sons Inc. New York, 24- Lever,A.B.P. (1968).Inorganic Electronic Sp ectroscopy , New York, 660 :15Inor g .chem. )1916( S.C. ,Cummings M .S. and,Holtman -52 26- Skop enko,V.V. ; Fristskii, I.O.; lemp leka, 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., Inor g.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) S ome physical propertie s of the complexes and their reactants quantities. dec: decomposition Table (2): I.R spectral data of the ligand and its complexes (cmˉ¹) Compo und dec om position tem pera ture 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): Electroni c spectral data and conductance me asurement in DMF as asolvant Assignment Λm s.cm 2 .mole -1 ε max molar -1 cm -1 nm λ Compound π→π * n→π * - 1121 301 (H4L) 4 T1(p) ← 4 A2(f) 23.5 403 505 342 430 [Co(H2L)] 1 B1g← 1 A1 g 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) S pectrum of the ligand Fig. (1a): The(I.R) S pectrum of [(Ni (H2L)] complex IBN AL- HAITHAM J. FO R PURE & APPL. SC I VO L.22 (3) 2009 Fig. (1b):The(I.R) S pectrum of [(Cu (H2L)] complex Fig. (1c): The (I.R) S pectrum of [Cd(H2L)] complex Fig(2) The (UV-Vis)S pectrum 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) S pectrum 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 i g u r e ( 3 ) t h e s u g g e s t e d s t r u c t u r e f o r t h e M ( H 2 L ) c o m p l e x e s M = C o , Z n ,C d NN C HH C O O H O H O N i f i g u r e ( 4 ) t h e s u g g e s t e d s t r u c t u r e o f t h e N i ( H 2 L ) c o m p l e 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 جامعة بغداد ،كلیة التربیة ابن الهیثمقسم الكیمیاء ، الخالصة N2O2 الجدید الرباعي السن نوعتضمن البحث تحضیر اللیكند Bis-1,2-(2,4-dihydroxy benzy lediene phy linediamine =(H4L) وذلك من مفاعلة بعض ایونات العناصر مفاعلة اللیكند مع ثم 2,4- Dihy droxy benzaldehy d مع) (o-p henylene diamine) )Co ll , Ni ll ,Cu l l , Zn ll , Cd ll تكونت اذ ،المیثانول وسطا للتفاعل وبوجود هیدروكسید البوتاسیوم قاعدة المعباست) M]الصیغة العامة يسلسلة من المعقدات ذ (H2L)] . ،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