IBN AL- HAITHAM J. FO R PURE & APPL. SC I VO L.22 (3) 2009 Preparation and Structural Studies of new Metal Complexes with 2-N(4- N,N- dimethyl benzyliden ) 5 - (p- methoxy phenyl)- 1,3,4- thiodiazole S. K. Abraheim , Sh. R. Bakir , M. F. Alias Department of Chemistry , College of Science for Women , University of Baghdad Abstract A new Schiff base, 2-N( 4- N,N – dimethyl benzyliden )5 – (p- methoxy phenyl) – 1,3,4- thiodiazol ,and their metal complexes Cu (Π) ,Ni (Π), Fe (III) , Pd (Π) , P t (IV) , Zn(Π) ,V(IV) and Co (Π) , were synthesized. T he prepared complexes were ident ified and their structural geometries were suggested by using flam atomic absorption technique , FT-IR and Uv-Vis spect roscopy, in addition to magnetic susceptibility and conductivity measurements. The study of the nature of the complexes formed in ethanol solution , following the mole rat io method , gave results which were compared successfully with those obtained from the isolated solid state studied. Structural geometries of compounds were also suggested in gas phase by using theoret ical treatments , using HyperChem-6 program for the molecular mechanics and semi- empirical calculations. T he heat of formation (∆Hƒ °) and binding energy (∆Eb) for the free ligand and their metal complexes were calculated by PM3 and AMBER met hods, P M3 was used to evaluate the vibrat ion spect ra of schiff base and to compare the theoret ically calculated wave numbers with exprimental values by using 2- amino- 5 (p- methoxy phenyl)-1,3,4- thiodiazole as authentic compound. The theoret ically obtained frequencies agreed calculation helped to assign unambiguously the most diagnostic bands. Introduction During the past two decades,a considerable at tention has been baid to the chemistry of the metal complexes of schiff bases (SB) containing nitrogen and other donors, this may be at tributed to their stability , biological act ivity and potential applicat ion in many fields such as oxidat ion catalysis, elect ro chemistry, etc (1-3). SB derived from sulfa durgs were successfully used for the bacteriastatic act ivit ies (4), and on the other side SB have been a great importance in the visual process (5), in addition to the react ion that involves removing the amino group by enzymic effect (enzymatic transition reaction), and some- B6.Catalysed react ion , as well as used as reversible oxygen carries (4). Another, path way of SB is involved in the metsbolism of Aflat oxin , produced by the funqi Aspergillus flavus, which grows on peanuts, is an extremely potent carcinogen capable of inducting liver cancer. It inhibits both replicat ion and transcript of DNA (6). SB are well known to have pronounced biological act ivit ies(7). T he biological act ivity of SB is attributed to the formation of stable chalets with t ransition metals present in cell (8) Their ready synthesis and myriod propert ies have contributed greatly to their popularity and to the study of many biological systems. Many of the physiologically active compounds of SB find applicat ions in the t reatment of several diseas (9,10). Bidentate and tridentate SB were among ligands that are extensively used for preparing metal complexes. T hese ligands are described according to their donor set NN, NO, NNO, NNS, NOO and NSO donors sets (11,12) The complexes of SB ligands have received a great deal of at tention during the last years to prepare new sets of these bases and their complexes , these complexes have proven to be ant itumor and have carcinostat ic activity (13,14). Experimental A- Materials , Physical Measuements and Analysis IBN AL- HAITHAM J. FO R PURE & APPL. SC I VO L.22 (3) 2009 All chemicals were of the highest purity and were used as received. Melt ing points were recorded on Gallen Kamp melting point apparat us and were uncorrected. FT-IR spect ra were recorded by using FT-IR 8400shimadzu in the range of (4000-200)cm-1 and samples were measured as CsI disc. Elect ronic spect ra were obtained by using (UV - 160) Shimadzu spect rophotometer at room temperat ure , using ethanol as a solvent. The metal cont ent was estimated spect rometriclly by using atomic absorption shimadzu AA670 spectrophotometer. Conductivity measurements were obtained by using (WTW) conductometer, these measurments were obtained in DMF solvent by using concentrat ion 10-3M at 25c°. Magnet ic susceptibility measurements were obtained at 25c° on the solid state appling Faraday,s meathod using Bruker BM6 instrument . B- Preparation the Compounds 1- Preparation of the Ligand The method that was used to prepar the 2-amino -5(p-methoxy phenyl)-1,3,4- thiodiazol (AM) was reported elsewhere (15). T he Schiff base (L) was prepared according to the following:- (AM) (0.05 mmol, 5.17g) was dissolved in 15 ml of Absolute ethanol and N,N- dimethyl benzyldehyde (3.7g , 0.05 mole) in 10 ml of the same solvent was added, with drop of glycial acetic acid, the react ion mixt ure was refluxed for (4) hours, aft er that , t he mixt ure was cooling at room temperat ure, then , left over night in a refrigerator, the separated solid was filt ered and crystallized from ethanol. T he physical propert ies of the (L) was listed in table (1) The structuctural formula of a new ligand may be suggested as follows CH3 NN S NOHCCH3O NH2 CH3 CH3 NN S NCH3O CH3 2-amino-5(p-methoxy phenyl)-1,3,4 thiodiazol 2-N(4-N,Ndimethyl benzyliden)-5-(p-methoxy phenyl)-1,3,4 thiodiazol N,Ndimethyl benzaldehyed re fl u x e t h a n o l N=C H 2- Prepartion of Complexes One general procedure was adoped , as follows: The salts of (VOSO4.H2O),CoCl2.6H2O ,Cu(NO3)2 3H2O ,PdCl2(PhCN)2 ,Ni(NO3)2 .6H2O, Fe(NO3)2 .9H2O , H2Pt Cl6.6H2O and Zn(CH3COO)2.2H2O were dissolved in ethanol and added to an ethanol solution of schiff base in (1 : 2) or (1 : 1) mole rat io respect ively with stirring. T he mixt ure was heated under refluxe for (4) hours. During this period the precipit at ion was a completed form . T he precipit at ion was then collected by filt rat ion , washed with ethanol and dried under vaccum. All t hese complexes were analyzed by using different available technigues, t he physical propert ies of these compounds are listed in table(1). C-S tudy of Complex Formation in S olution Complexes of the schiff base with metal ions were studied in solution by using ethanol as a solvent, in order to determined [M:L] rat io in the complex following molar rat io method (16). A series of solutions were prepared by having a constant concentrat ion 10-3M of metal ion and the ligand. The [M:L] rat io was determined from the relat ionship between the absorption of the absorbed light and the mole rat io of [M:L]. T he results of complexes formation in a solution were listed in tabel (1). D- Programs Used in Theoretical Calculation 1- HyperChem-6 IBN AL- HAITHAM J. FO R PURE & APPL. SC I VO L.22 (3) 2009 It is a sophisticaled molecular modeler , editor and powerful computional package, that is known for its quality, flexibility and ease of use, uniting 3D visualizat ion and animat ion with quantum chemical calculat ions, mechanic and dynamic. HyperChem-6 can plot orbital where funct ions result from semi- empirical quantum mechanical calculation, as well as the electrostat ic pot ential , the total charge density or the total spin density can also be determined during a semi- empirical calculation. T his information is useful in determining react ivity and correlat ing calculation results with the experimental data. 2- Types of Calculation •Single point calculation that determines the molecular energy and properties for a given fixed geometry. •Geometry optimization calculations employ energy minimization algorithms to locate stable structures. •Vibrat ional frequency calculations to find the normal vibrational modes of an optimized structure . The vibrational spectrum can be displayed and the vibrational motions associated with specific transitions can be animated (17). 3- Computional Methods a-Semi- empirical Quantum Mechanics HyperChem offers t en semi- empirical molecular orbita methods, with opt ions for organic and main group compounds, for transition metal complexes and spectral simulation (18). PM3 were used for the calculat ion of heat of formation and binding energy for all metal complexes except platinum (IV) and vanadium (IV) complexes. b- Molecular Mechanics It has three important concepts. Funct ional form , atoms types and parameter sets. Each molecular mechanics method has its own funct ional form (Assisted Model Building and Energy Refinement ) (AMBER) is based on a force field (19). AMBER was used for the calculat ion of the binding energy and heat of formation of platinum(IV) and vanadium(IV) complexes. Result and Discussion A- Elemental Analyses The importance of preparing a new Schiff base arises from their virility as start ing meterials for the synthesis of many complexes especially with t ransition metal ions. T he physical and analytical data of the ligand and metal complexes are given in table (1). T he results obtained from metal analysis are in a satisfactory agreement with the calculated values .T he suggested molecular formula was also supported by spect ral measurement as well as magnet ic moment s . B- Infrared Spectroscopic Study 1- There is no appreciable change that took place in the absorption of νs(COC)and νas(COC) modes in the monomeric zinc, palladium and cobalt complexes, which exclude the possibility oxygen atom of methoxy group part icipat ion in coordination . Furthermore , t here is a change in frequency and intensity of νC = N and νN – N bands, this behaviour refers t o coordinate modes of the ligand through nit rogen of isomethane group and nit rogen of the thiodiazole ring (20) ,table (2). 2- The ligand behaviour is a different coordinate, i.e. through oxygen of methoxy group and nit rogen of isomethan as a bridge for the dimeric iron, platinum, cupper and vanadium complexes or through sulfur at om of thiodiazale for the nickel complex . T he other behaviour of the ligand took place as abidentate through N,N or N,S atoms for the complexes cupper, vanadium , platinum and nickel ion, while the ligand behaves as a monodetate coordinat e through nitrogen of isomethane only in iron complex (20). 3- νV = O stret ching mode in vanadium complex was observed at 979 cm-1 as a strong band. Coordinat ion of sulfat e ion this complex was a bserved as a bidentate behaviour (21). 4- These absorptions were further supported by the appearance frequencies of νM-S νM-O νM-N and νM-Cl respect ivly (20, 22). 5- A braod band was observed around (3450-3510) cm-1 in the spect ra of the complexes , assigned to a νO-H and suggested the presence of water or ethanol molecules in the crystal lattic of the complexes (23). IBN AL- HAITHAM J. FO R PURE & APPL. SC I VO L.22 (3) 2009 C-Electronic Spectroscopy Study 1-CuL Complex The electronic spect ra of cupper complex showed one broad absorption band in the region around 12987 cm-1 which was at tributed to 2B1g → 2A1g t ransition table (3). T he position of this band is in an agreement with what is reported for highly distort ion octahedral geometry (24,25). The elect ronic spect ra coupled with magnetic moment (1.03 BM) studies indicate squar planner geometric around Cu(II) complex (26),conductivity measurement showed that the complex was ionic.T he structure of this complex can be suggested as bellow. Cu N N S R O CH 3 N C-RNN S NN S O H 3 C N Cu N N S R R=C 6 H 4 N(CH 3 ) 2 R=C 6 H 4 OCH 3 (NO 3 ) 4 .EtOH = = CH R N = CH R N = CH R 2-CoL Complex The blue – greenish cobalt(II) complex with ligand showed a magnetic moment of (4.8BM), which indicates a high – spin type complex . Elect ronic spect rum in ethanol solution exhibited a split band in the range of (17000-14000) cm-1, the split band is a t ypical t etrahedral spectra type and can be assigned as 4A2→4T 1(p) (ν3) , and in addition there is a band at 3409 cm-1 which was taking from IR and can be assigned to 4A2→4T 2(F) (ν2) transition (27, 28). The colour as well as the magnetic moment further indicated tetrahedral geometry. The (ν2) and various ligand field parameter were calculated by reference t o T anaba- Sugano diagram for d7 configurat io table (3).The calculation of the spin – orbit coupling constant(x) was µob s = µs.o -15.59 λ\ / 10 Dq weher µobs = The observed effect ive magnet ic µs.o = The electronic spin only magnetic moment The resulting value (λ\ = -218.5 cm-1) ,this value shows the present complex to be distorted tetrahedral (29).The nephelauxet ic factor β was calculated and found to be (0.63) indicat ing high degree of covalence in the bonding of ligand- donor atoms with cobalt (II) ion. T he molar conductance showed that the complex is elect rolyt e, and the following structural may be proposed. IBN AL- HAITHAM J. FO R PURE & APPL. SC I VO L.22 (3) 2009 C o N N S NN S R N R R = C 6 H 4 N ( C H 3 ) 2 R = C 6 H 4 O C H 3 = ( N O 3 ) 2 .3 C 2 H 5 O H N = H R C C H R 3-NiL Complex The elect ronic spect ral data , and their assignment as well as the calculated ligand field parameters for nickel thiodaizal benzyliden , are shown in table (3). Considering these data and comparisom with a large number of published works (30- 32), led to the proposal of the following dimeric structure. R N = C - RN N S N i R - C = N N N S R R . (N O 3 ) 4 .H 2 O N = C - RN N S N i R - C = N N N S R R = C 6 H 4 O C H 3 R = C 6 H 4 N (C H 3 ) 2 H H H H Which stat isfies the EAN configurat ion for Ni . The ligand field parameters B/,β and 10Dq, were calculated by fit t ing the rat io of the observed two bands, i.e ν2 and ν3 to T -S. diagram as shown in d8 configurat ion. T he calculation of spin- orbit coupling constant λ was µobs=µs.o( 1- 4λ\ 10Dq ) 3.35= 2.83 (1- �λ\ ����� ) The resulting value = -3186.3 cm-1 , shows the present nickel complex to be tetragonal distortion (33) or this value is well showing tetragonal distort ion.T he magnet ic measurement is (3.35BM), which shows the complex to be paramagnet ic and conductivity studied show that the complex is elect rolyt e. IBN AL- HAITHAM J. FO R PURE & APPL. SC I VO L.22 (3) 2009 4-PtL Complex The electronic spect rum of the platinum (IV) shows three bands , the first weak on appeared at 13315cm-1 can be assigned to the forbidden t ransition 1A1g →3T 1g and other two bands with higher int ensity can be assigned to the following t ransition in octahedral enviromneut (34). 1A1g →1T 1g 1A1g →1T 2g This coordination type is common for Pt(IV) complexes (33,34) , the study of conductivity behaviour in DMF shows the complex to be ionic . T he magnetic measurement data is (0.82 BM) which shows the complex to be diamagnet ic, table (3), therefore, the following structure can be suggested: Pt N=CR N N S R Cl Cl NN S NN S R CH 3 Pt N N S R-C=N Cl Cl R=C 6 H 4 OCH 3 R=C 6 H 4 N(CH 3 ) 2 O CH 3 N R-C N C-R O Cl 4 .4EtOH = = H H H H 5-VL Complex Vanadium complex showed two bands related to squar pyramide vanadium complex (34,35). They were observed at 12755, 17699 cm-1 table (3) for the first and second transition and were assigend to 2B2g→2Eg and 2B2g→2B1g transition respectively (27,29,26,34). T he magnet ic moment (1.3 BM) is lower than spin only value, this is due to spin- coupling (29, 36). Conductivity in DMF showed that the complex was ionic, According to this ,the following structural formula can be suggested. V O O O S O O N C-R O CH 3 NN S NN S O CH 3 N R-C V O NN S R R=C 6 H 4 N(CH 3 ) 2 R=C 6 H 4 OCH 3 SO 4 .H 2 O = = = = H H N= CH R 6-ZnL Complex The prepared complex is colourless and diamagnet ic which is expected for d10 ion . The UV-Vis spect rum of the compound shows arelative change in the band posit ion compared to that of the free .T he conductivity measurement for this complex in DMF at 25°C showed to be nonconducting (22µs.cm-1).The most propable structral of this complex is tetrahedral as shown bellow. IBN AL- HAITHAM J. FO R PURE & APPL. SC I VO L.22 (3) 2009 Z n O C - C H 3 O O C - C H 3 O NN S R = C 6 H 4 N ( C H 3 ) 2 R = C 6 H 4 O C H 3 . 3 E t O H = = R N = C H R 7-FeL Complex The magnetic measurement shows the iron ion in its orange complex to be ahigh spin paramagnetic (5.32 BM), of d5 configurat ion T his suggestion was supported by the number of maxima observed in the electronic spect rum of the complex , which show two maxima bands which may be assigned to transition 6A1g→4T 2g(G), 6A1g→4A1g+4Eg(G) as shown in table (3) (33,37). The ν1 and racah parameter β., and the value of 10Dq, which were calculated by reference to T anab- Sugamo for d5 configurat ion. T he conductivity measurement in DMF show the complex to be non- elect rolyt e. Depending on this information, the following structural may be proposed. Fe Fe ONO 2 ONO 2 ONO 2 ONO 2 ONO 2 N C-R R NN S O CH 3 N R-C NN S NN S N C-R O H 3 C N R -C NN S R .H 2 O = = = = R=C 6 H 4 N(CH 3 ) 2 R=C 6 H 4 OCH 3 H H H H O2NO 8-PdL Complex The brown palladium complex shows strong charge transfer bands which was extended to the visible region , so the ligand field bands could not be estabished easily . Nevert hless two weak bands at 22471 and 28169 cm-1 table (3) may be assigned to the t ransition 1A1g→1B1g (2a1g→1a1g. 1b1g) and 1A1g→1Eg (4eg. 2a1g→3eg. 2a1g→3eg. 2a1g.1b1g) respect ively, for spin- paired d8 squar planner configurat ion with magnetic moment value of (0.00 BM). This assignment was made by reference t o know palladium complex with squar planner sterochemistry , and came in a good agreement with published data (34,33). Conductivity value confirmed the ionic structure . Depending on this finding the following structural formula of this complex may be proposed. IBN AL- HAITHAM J. FO R PURE & APPL. SC I VO L.22 (3) 2009 R N=C-RN N S Pd Cl 2 . 4C 2 H 5 OH N N N S R-C R R=C 6 H 4 OCH 3 R=C 6 H 4 N(CH 3 ) 2 = H H D- S olution S tudy Molar rat io method was followed to detemined the M : L rat io . The result of complexes in ethanol solution , suggest that the metal to ligand rat io was (1 : 2) , which are dimeric in nature for the (cupper, platinum, nickel ), and monemer for palladium and cobalt complexes , and (1 : 1.7) for vanadium complex, while (1 : 1) for the zinc and iron metal complexes , which were comparable to these obtained from isolat ed solid study, t able (1). E- Theoretical S tudies (i) The program HyperChem-6 was used for the semi- empirical and molecular mechanic calculations, at optimized geometries energies, the result on PM3 and AMBER methods of calculation in gas phase for the heat of formantion (∆H° ƒ) and binding energy (∆Eb) for the ligands and their complexes were calculated and tabulated in table (4). Also PM3 was used for the evalution of the vibrational spectra of the AM and Schiff base to compare the theoretically calculated wave numbers with the experimental values. Theoretically calculated wave numbers for these ligands showed that some deviat ions from the experimental values, these deviations are generally acceptable in theoretical calculations and are described in t able(2) and (5) and the figs.(1) (2). (ii) Electrostatic Potential (E.P.):- Electron distribution governs the electrostic potential of molecules and describes the interaction of energy of the molecular system with a postive point charge, so it is usef ul for finding sites of react ion in a molecule positive charged species tend to attack a molecule where the E.P. is strongly negative electrophilic attack (38,39). (E.P.) of free ligand was calculated and plotted as 2D contour to investigate the reactive sites of the molecules Fig(3), and one can interpret the stereochemistry and rates of many reactions involving soft electrophiles and nuclephiles in terms of the properties of frontier orbitals(HOMO and LUMO). Overlap between the HOMO and LUMO is a govering factor in many reactions. The HOMO and LUMO values were plotted as 2D contour to get more information about these molecules. The results of calculation showed that the LUMO of transit ion metal ion prefer to react with the HOMO of sulfur and nitrogen atoms of Schiff base ligand. (iii) Optimized Geometries Energy of Metal Complexes for Schiff Base All theoretically probable structures of metal complexes with schiff base were calculated to search for the most probable model building stable structure , these shapes fig.(4), show the calculated optima geometries for (L) and their metal complexes. The results of PM3 method of calculation in gas phase for the binding energies and heat of formation of Co(II), Cu(II), Pd(II), Zn(II), Ni(II) and Fe(III) , while AMBER method was used to calculate the binding energies which is equal to heat formation for both Pt(IV) and V(IV) complexes , and are described in table (4). IBN AL- HAITHAM J. FO R PURE & APPL. SC I VO L.22 (3) 2009 References 1. Tai,X.; Yin, X.; Chen, Q. and Tan,M. (2003). Molecules, 8, 439 . 2. .Miliani, F.; Casellato, U.; Vigato, P. A.and Vidali, M. (1985). Inorg. Chem. , Acta. 103, 15. 3. Shady,H.; Ragab, F. A. and Aly,E. I. (1988). Kimphrmzh, 16 (12), 1466, (1989). Chem Alost , 110, 173068W 4. Echhor,G.L. (1993). "Inorganic Biochemistry" Elsevier Scientific Puplishing Company, Amusterdam. 5. Mohomed,A.Z.; (1992). M. SC. Thesis, university of mosul . 6. Massey,T.E.; Stewart , R. K.; Dainels, (1995) J. M. and L. Liv, pro. Soc. Exp. Biol. Med, 205-213. 7. Sahai,R. K.; Kushwaha, S.S.and Chaudhary, A. K. (1989). J. Indian chem, 19:13,844 . 8. Banerjea ,O. (1980)."Coordination Chemistry, 20" , Pergaman Press. IUPAC, Oxford, New York. 9. Lai, Keemti; Shukla,P .K. (1981). J. Indian Chem. 58:115 . 10. Tren,Mats. T. M. (1953)."Antibiotics of chemotherapy" , 3,941. 11. Freyberg, D. P. and Mockler,G. M. (1976). J. Chem. Soc. Daltontrans, 5, 445 . 12. Goodiwn,J.A. and Wilson,L. (1989).J. Inorg. Chem. , 28, 42. 13. Davar Boghaei,M. and Sajjed,M. (2000).J. Molecular Catalysis A: Chemical, 179, 41. 14. Shrivastava ,V. S.; Bhasin ,C. P. and Saxena,G. C. (1989).J. Indian Chem. Soc. , 63, 865 . 15. Shafiee,A. ; Nami, E.; Amnsobi, P.; Forommav,A. and Shekar, M. (1995).J. Hetro Cyclic Chem., 32,p.1235 . 16. . Skooge ,D. A. , (1988)."Fundemental of Analytical Chemistry", 5th Ed. New York. 17. Foresman, J. and . Frish. ,C., (1996). "Exploring Chemistry with Electronic Structure Methods" 2nd Ed.,Gaussian Inc., Pittsburgh, PA. 18. Fried, Howard L.; and Souers,P.; (1999).CHEETAH 2-Ovsers Mannal, Lawrence Livermore National Laboratory. 19. Atkins P. and Friedman , R. (1997)."Molecular Quantum Mechainics"; 3rd Ed. ; New York; Oxford University press Inc ; NY . 20. Nakamoto ,N. (1997). " Infrared Spectra of Inorganic and Coordination Compounds". 6th ed , Wiley Intrescience, New York. 21. . Kumari ,U. N. and Singh ,C. P. (1990). "Oxovanadium (IV) Complexes with thiohydrazide derivat ives" J. Ind. Chem. Soc. Lvu (8). 22. Singh ,B. and Thakup ,K. P. (1973). J. Inorg. Nud. Chem., 36, 1735. 23. Silvertistein,R. M.; Bassler ,G. C. and Morrill,T . C. (1981). "Spect rometric Ident ification of Organic Compounds", 4th ed., John Wiley and Sons. 24. Hiremath, A. C. ; Halli, M. B. and Huggi, N. V. ; (1986). J Ind. Chem. Soc. ; Lx III ; 374. 25. Nawar, N. E. ; Khattab, M. A. and El. Kaddan, A. H. ; (1996). J. Ind. Chem., LXV, 308. 26. Burger , K. ; (1956) ; "Magneto Chemistry" 2nd . Ed. ; Ins.; Publishers; Ltd. ; Londo. 27. Carlin, R. L. ; ; (1965). "Transition Metal chemistry"; 1, Marcel Dekker N. 28. Hedwy, S. ; (1978).Inorg. Chem.; 29;155 . 29. Lever,A.B.P.(1986)."Inorganic Electronic Spectroscopy", Ansterdam London . 30. Aggarwal ,R.C. and Yadava,R. B. S. Trans. (1979) Met. Chem., 1, 139. 31. Wuu ,Y. M. and Peng,S. M. (1980) J. , Inorg. Nucl. Chem. ,42,205. 32. Deshmuke ,K. and Bhobe, R. A. (1979)J. Inorg. Nucl. Chem. ,40, 134. 33. Jorgeuson, C. K. (1968)."Absorption Spectra and Chemical bonding in Complexes"; pergaman press. 34. Figgis, B., N.,(1966). "Introduction to Ligand Field"; Interscience; New York . 35. ao ,P. V. and Rao,N. R. (1988).Ind. J. of Chem. ; 27A,73. 36. Mahta,P. K. ; Gahlot,A. (1986). J. Ind. Chem. Soc. , LXIII (2). 37. Bailer,J. C.; Emeleus, H. J. and Nypholm, R. (1973). "Comprehensive Inorganic Chemistry", Perganmon Press. 38. Steword,J .J .P .; MOPAC 2000 VIO for windows (Singie), MO20-AS-W, Fujitsu STEM EUROPE. 39. Anderson,W .P .; Behm, P. and Glennon,T .M. , (1997).J .Phys. Chem.,vol. (101) IBN AL- HAITHAM J. FO R PURE & APPL. SC I VO L.22 (3) 2009 d : decomposed poin O A C =C H 3-C -O = O Table (1): Physical data for the ligand (L) and their metal complexes Suggest Molecular formula Metal to ligand ratio Atomi c Abs. Found (Cal.) Yiel d % m.p C° Colour Co mp. C18 H18 N4 SO ــــــ 114 84.0 ــ Pale Orang L [Cu2(L)4](NO3)4. C2H5OH 1 : 2 5.58 (6.70) 50.0 84 Pale Brown Cu L [Co(L)2](NO3)2.3 C2H5OH 1 : 2 5.29 (4.51) 75.8 63 d Bluish- Green Co L [Ni2(L)2]2(NO3)4. H2O 1 : 2 6.78 (7.39) 51.7 160 Dark Orang Ni L [Pt(L)2Cl2]2Cl4.4 C2H5OH 1:2 17.61 (17.88 ) 40.0 204 Dark Orang Pt L [(VO)2(L)3SO4]S O4.H2O 1:1.7 ــــــ ــ 44.4 > 360 Olive V L [Zn(L)(OAC)2].3 C2H5OH 1 :1 4.49 (5.33) 42.8 122 -23 Orang Zn L [Fe(L)2(NO3)3]2.2 H2O 1:1 .96 (5.90) 64.0 65 Reddis h- orang Fe L [Pd(L)2]Cl2.4C2H 5OH 1 : 2 10.2 (9.8) 84.0 201 Dark Brown Pd L IBN AL- HAITHAM J. FO R PURE & APPL. SC I VO L.22 (3) 2009 Fig. (1) The Calculated Vibrational Frequencies of AM Fig. (2) The Calculated Vibrational Frequencies of Schiff Base L νN-N( 1441.58) νsymΝH2( 3426.39) νasyΝH2( 3534.00) νsymC-H( 3029.29) νasyC-H (3041.60) C-S ( 839.08) νN-C-N( 1330.84) νNCS(1238. 01) νNCS( 1014.63) νsymOCH3 (1003.63) νasyOCH3 ( 1281.19) νC-S-C( 1166.09) C-N( 879.42) δNH2(1652. 39) νC-S (717.39) νN-N(1439.56 ) νC=Niso (1628.62) νC=Nring (1576.88) νC=Nring ( 1568.45) νAr-N ( 1328.25) νC-S-C( 1155.76) νOCH3sy (1099.09) νOCH3asy (1293.73) νNCS (1166.13) νNCS( 1073.69) νN-C-N (1325.22) IBN AL- HAITHAM J. FO R PURE & APPL. SC I VO L.22 (3) 2009 Fig. (3): HOMO and Electrostatic Potential as 2D Contours for L Fig. (4): Conformational Structure of AM, L and their Complexes Electrostatic Potential L HOMO of L AM L CoL VL ZnL CuL IBN AL- HAITHAM J. FO R PURE & APPL. SC I VO L.22 (3) 2009 NiL PtL PdL FeL Table (3) : Electronic spectra, conductance and magnetic moment, for metal complexes of L Co mp. Bands cm-1 Assignm ent B B\ Dq /B\ β 10D q 15B\ µe ff µs c m - 1 Co L 3409 (5541) cal. 15460 av 4A2 → 4 T2(F) 4A2 → 4 T1(F) 4A2 → 4T1(P) 11 28 718 .3 0.5 0. 63 3663 .3 107 74.5 4. 8 18 2 Cu L 12987 2 B1g → 2A1g 1. 03 21 V L 12755 17699 2B2g → 2 Eg 2B2g → 2B1g 1. 3 18 2 Pt L 13315 23148 27397 1 A1g → 3T1g 1 A1g → 1T1g 1A1g → 1 T1g 0. 82 20 5 Ni L 13850 1067.2 18148 23529 (26250 )cal. 3 A2g → 1Eg 3 A2g → 3T2g(F) 3A2g → 3 T1g(F) 3A2g →3 T1g(P) 10 80 102 5.5 1.0 5 0. 94 1076 7 153 82 3. 35 30 6 Fe L 99300 cal. (88268 ) 14814 21834 6A1g→4 T1g(G ) 6A1g→4 T2g(G ) 6 A1g→ 4 T1g+ 4Eg 13 00 677 .8 1.7 0. 52 1152 0 101 67 5. 32 21 Pd L 22471 28169 1A1g → 1 B1g 1A1g → 1 E1g 0. 00 69 Table (2) The most diagnostic FT- IR bands for the L and its metal complexes M-O)M-S)(M-N)Ar-N)(N-N)(υ)NCN(υring) (C=Nυ )CS(υCSC) ()(NCS υiso ) (C=Nυ Comp . 1311. 5 144261373.21589.2 1527.5 7321164. 9 1051 1120 1658.6L 4785631311. 5 1442 137 3.2 1604.6 1535.2 .17251172. 6 1064 1118.6 1647 Co L 4865051311144 2 137 3.2 1596.9 1527.5 725.111741070 1110.9 1649 Ni L 447.4 5161311. 5 148 1.2 137 3.2 1604.6 1535.2 72911681058 1118.6 1647 Zn L 478.3 516.8 1485 1369 1596.9 1535.2 732.911681049.2 1110.0 2 1647 Cu L 532.3470.6578.01311. 5 1460 1373.21604.6 1542.9 7500.3 118 1063 1126.3 1697.2Pt L 54013111485 1373 1604 1504.3 73311671057 1141.7 1646 V L 48651613101442 1373 1596 1520 725.11172. 6 1033 1126 1650 Pd L 416 5201310 1373 1590 1530 73311661050 1125 1627 Fe L Table (4): Conformation Energetic (in KJ.Mol-1) for L and their metal complexes IBN AL- HAITHAM J. FO R PURE & APPL. SC I VO L.22 (3) 2009 AMBER PM3 Conform ation EbΔ =ºHfΔ EbΔ ºHfΔ -2417.8692 54.01773 AM - 4491.4313635 -100.3836365 L -9447.4652 -109.3332 CoL -9328.1735578 -180.8655578 NiL -18212.6603680 315.9996320- CuL 469.320923 PtL -377002.125000 VL -5884.83965 -27.446653 ZnL -9122.034 151.5953 PdL W he re : * : E xp er im en ta l fr eq u en cy ** : T ho re ti ca l fr eq ue n cy ** *: E rr or % d ue to m ai n d if fe re n ce i n yh e ex pe ri m en ta l m ea su re m en ts a nd th eo re ti ca l tr ea tm en t o f v ib ra ti on al s pe ct ru m . ( 13 28 2 )** - υ A r- N T ab le ( 5) :C om p ar is on o f ex p er im en ta l an d th eo re ti ca l vi b ra ti on al f re q u en ci es (2 97 0, 28 94 )** 10 35 ) (1 28 1 , 10 03 .6 )** (- 2 .3 ,- υ O C H (1 32 5 2) ** * ) (1 33 0 )** (4 .6 υ N C N (7 17 . 3) ** * (8 39 ) ** ( - 8 υ C = S (1 15 5. 7) ** ) (1 16 6 )** (0 υ C S C (1 43 9 5) ** * ) (1 44 1 )** (1 υ N - N (1 07 3. 6 , 11 66 .1 )** 11 22 ) (1 23 8. 01 , 10 14 .6 )* * (- 9 .0 , 9 υ N C S (1 62 8. 6 )** - υ C = N is - 31 72 ) (3 53 4 , 34 26 )** (- 7 .0 , 8 υ N H 2 L 1 A M S y m b . لتطبیقیة الصرفة للعلوم الھیثم ابن مجلة 2009 )3( 22المجلد وا – N-2 )4 ،N ،Nتحضیر ودراسة تراكیب معقدات فلزیة جدیدة مع – 4، 3، 1 –) میثوكسي فینیلP - (– 5) ثنائي مثیل بنزیلدین ثایودیازول محاسن فیصل الیاس، شیماء رجب باقر ، سرى خلیل ابراھیم جامعة بغداد، كلیة العلوم للبنات قسم الكیمیاء، الخالصة – 4 ، 3 ، 1 – )بـارا میثوكسـي فینیـل – 5) ثنـائي مثیـل بنزیلـدین – N-2 )4، N، N تـم تحضـیر اللیكانـد ه مـع االیونــ ـاسثایودیـازول ومعقداتــ ،)III(والحدیــد ،)II(والزنــك ،IV)(والبالتـین ،)II( والبالدیــوم ،)II(والنیكـل ،)II(ات النحـ شــخص وعــین الشــكل الهندســي للمركبــات المحضــرة بأســتخدام األجهــزه الطیفیــه ، األشــعة IV (0(والفنــادیوم،) II(والكوبلـت ـا ال عـنضــفالمرئیـة –تحـت الحمـراء واألشـعة فـوق البنفسـجیة درس 0قیـاس الحساسـیة المغناطیسـة والتوصـیل الكهربـائي لهـ مقاربة مع النتائج التي تم الحصـول علیهـا ااعطت نتائجاذ ،حالیل بأتباع طریقة النسب المولیةطبیعة المعقد المتكون في الم .لة الصلبة المعزولةابالح بتطبیـق المیكانیـك ) HyperChem-6(اجریت معالجة تكوین المعقدات نظریـًا فـي الطـور الغـازي باسـتخدام برنـامج PMالجزیئـي والشـبه التجریبــي فـي الحســاب وذلـك باسـتخدام الــدوال 3 ،AM BER لحسـاب حــرارة التكـوین(∆Hƒ وطاقــة (° ة حــرارة ) Eb∆(التــرابط ـتاتیكي لبیــان المواقــع .كلفــن للیكانــد ومعقداتــه المحضــرة 298وبدرجــ ، كــذلك حســب الجهــد األلكتروسـ PMریـًا وبأسـتخدام الدالـة لتــردد األهتـزازي نظشـف وجـرى حسـاب ا الفعالـة لقاعـدة ا مـع القـیم المقاســه 3 لقاعــدة شـف ومقارنتهـ ـارا میثوكسـي فینیــل ( 5 –امینـو -2عملیـًا بأســتخدام ووجــد أن هنـاك توافقــًا اقیاسـی اثایودیـازول مركبــ – 4، 3، 1 –) بـ 0كبیرًا بین القیم العملیة والمحسوبة نظریًا مع زیادة امكانیة تشخیص الحزم بشكل ادق