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. Bak ir , M. F. Alias Departme nt of Chemistry , College of Science for Women , Unive rsity of Baghdad Abstract A new Schiff base, 2- N( 4- N,N – dimet hyl benzyliden )5 – (p - met hoxy ph enyl) – 1,3,4- t hio diazol ,and t heir met al co mp lexes Cu (Π) ,Ni ( Π), Fe ( III) , P d (Π) , P t (IV) , Zn(Π) ,V(IV) and Co (Π) , were syn t hesized. T he prep ared co mp lexes were ident ified and their structural geometries were suggested by using flam at omic absorp t ion t echnique , FT -IR and Uv-Vis spect ro scop y, in addit ion t o magnet ic suscept ibility and con duct ivit y measurem ent s. T he st udy of t he n at ure of t he comp lexes fo rmed in et hanol solution , follo wing t he mo le rat io met hod , gave result s which were comp ared successfully wit h t hose obt ained from t he isolat ed solid st at e st udied. St ruct ural geomet ries of comp ounds were also suggested in gas ph ase by using t heor et ical t reat ment s , using HyperChem-6 pr ogram fo r t he mo lecular mechanics and semi- empirical calculation s. T he heat of fo rmat ion (∆Hƒ ° ) and binding energy (∆Eb) fo r t he free ligand and their metal comp lexes were calculat ed by P M3 and AMBER met ho ds, P M3 was used t o ev aluate t he vibrat ion spect ra of schiff base and t o comp are t he t heor et ically calculat ed wave numbers wit h expriment al values by using 2- amino - 5 (p - met ho xy ph enyl)-1 ,3,4- t hiodiazole as authent ic comp ound. T he t heor et ically obt ained frequencies agreed calculation helped t o assign unambiguously t he mo st diagnostic bands. Introduction During t he p ast t wo decades,a considerable at t ent ion has been baid to t he ch emistry of the metal comp lexes of schiff bases (S B) co nt aining nit ro gen an d ot her dono rs, t his m ay be at t ribut ed to their stabilit y , biolo gical act ivit y and po t ent ial applicat ion in many fields such as ox idat ion cat alysis, elect ro ch emistry , et c (1- 3) . S B derived from sulfa durgs were successfully used for t he bact eriastatic act ivit ies (4 ), an d on t he ot her side S B have been a great impo rt ance in t he v isual pro cess (5), in addit ion t o t he react ion t hat inv olves rem ov ing t he amino gro up by enzymic effect (en zymat ic t ran sition reaction), and some- B6.Cat alysed react ion , as well as used as reversible oxygen carries (4) . Anot her, pat h way of S B is inv olved in t he met sbolism of Aflat oxin , pr oduced by t he funqi Aspergillus flav us, which grows on peanut s, is an ex t rem ely pot ent carcinogen cap able of induct ing liver cancer. It inh ibit s bot h rep licat ion and t ran script of DNA (6 ). S B are well known t o have pro no unced biolo gical act ivit ies(7). T he biolo gical act ivit y of SB is at t ribut ed t o t he for mat ion of stable chalet s wit h t ran sition met als present in cell (8 ) T heir ready synt hesis an d myriod pro pert ies have co nt ribut ed great ly t o t heir pop ularit y and t o t he st udy of many biological systems. Many of the physiologically act ive co mp ounds of SB find ap plicat ion s in t he t reat ment of several diseas (9,10) . Bident at e an d trident at e S B were among ligands t hat are ext ensively used for prep arin g met al comp lexes. T hese ligands are described accor ding t o t heir dono r set NN, NO, NNO, NNS, NOO and NSO donors set s (11,12 ) T he co mp lexes of SB ligands have received a great deal of at t ent ion during t he last years t o pr epare new set s of t hese bases and t heir comp lexes , t hese comp lexes have proven to be ant it umo r and have carcin ost at ic act ivit y (13 ,14) . Experime ntal A- Materials , Physical Measuements and Anal ysis IBN AL- HAITHAM J. FO R PURE & APPL. SC I VO L.22 (3) 2009 All chemicals were of t he highest purit y an d were used as received. Melt ing poin t s were recorded on Gallen Kam p melt ing poin t ap parat us an d were unco rrect ed. FT -IR spect ra were recorded by using FT -IR 840 0shimadzu in t he ran ge of (4 000 -2 00 )cm -1 and samples were measured as CsI disc. Elect ro nic spect ra were obt ained by using (UV - 16 0) Shim adzu spect ro ph ot om et er at ro om t emperat ure , using et hano l as a solvent . T he met al co nt ent was est imat ed spect ro met riclly by using at omic absorp t ion shim adzu AA6 70 spect ro ph ot om et er. Con duct ivit y measurem ent s were obtained by using (W T W) conduct omet er, t hese measurment s were obt ained in DMF solvent by using concent rat ion 10 -3 M at 25c ° . Magnet ic suscept ibility measurem ent s were obtained at 25c ° on the solid stat e ap pling Faraday , s meat ho d using Bruker BM6 inst rumen t . B- Preparation the Compounds 1- Preparation of the Ligand T he met hod t hat was used to prep ar t he 2 -am ino -5(p -met hoxy ph enyl)-1,3,4- t hiodiazol (AM) was report ed elsewhere (15 ). T he Schiff base (L) was prep ared according t o t he follo wing:- (AM) (0 .05 mm ol, 5.17g) was dissolved in 15 ml of Absolut e et hanol and N,N- dimet hy l benzyldehyde (3.7g , 0.05 mole) in 10 ml of t he same solvent was added, wit h drop of glycial acetic acid, t he react ion mixt ure was refluxed fo r (4 ) ho urs, aft er t hat , t he mixt ure was cooling at ro om t emperat ure, t hen , left over night in a refrigerat or , t he separat ed solid was filt ered and crystallized from et hano l. T he phy sical pro pert ies of t he (L) was listed in t able (1) T he st ruct uct ural fo rmula o f a n ew ligand may be suggest ed 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 Comple xes One general pr ocedure was adoped , as fo llows: T he salts of (VOSO4.H2O),CoCl2.6H2O ,Cu(NO3)2 3H2O ,P dCl2(P hCN)2 ,Ni(NO3)2 .6H2O, Fe(NO3)2 .9H2O , H2P t Cl6.6H2O and Zn(CH3COO)2.2H2O were dissolved in et hano l and added to an et hanol solution of schiff base in (1 : 2) or (1 : 1 ) mo le rat io respect ively wit h st irring. T he mixt ure was heat ed under refluxe for (4) hours. During t his period the precipit at ion was a com plet ed form . T he precipit at ion was t hen co llected by filt rat ion , washed wit h et hano l and dried under v accum. All t hese comp lexes were an alyzed by using different av ailable t echnigues, t he physical pr opert ies of t hese comp ounds are listed in t able(1). C-S tudy of Complex Formation i n S oluti on Complexes of t he schiff base wit h met al ion s were studied in solution by using et hano l as a solvent , in order t o determ ined [M:L] rat io in t he co mp lex follo wing molar rat io method (16). A series of solution s were prep ared by having a constant co ncent rat ion 10 -3 M o f met al ion and the ligand. The [M:L] rat io was determ ined fro m t he relat ion ship between t he absorpt ion of t he absorbed light and the mo le rat io of [M:L]. T he result s of co mp lexes fo rmat ion in a solution were listed in t abel (1). D- Programs Used in Theoreti cal Calculation 1- HyperChe m-6 IBN AL- HAITHAM J . FO R PURE & APPL. SC I VO L.22 (3) 2009 It is a sophisticaled mo lecular modeler , editor an d powerful co mp ut ion al package, t hat is known fo r it s qualit y, flex ibility and ease of use, unit ing 3D visualizat ion and animat ion wit h quant um chemical calculat ion s, mechanic an d dynamic. HyperChem-6 can plot orbital where funct ion s result fro m semi- empirical quant um mechanical calculation , as well as t he elect ro stat ic pot ent ial , t he t ot al ch arge densit y or t he t ot al spin density can also be det erm ined during a semi- empirical calculation . T his informat ion is useful in determ inin g react ivit y an d co rrelat ing calculat ion result s wit h t he ex perim ent al dat a. 2- Types of Calculation •Single point calculation t hat det ermin es the mo lecular energy an d pr opert ies fo r a given fixed geometry. •Geometry opt imization calculat ions employ energy minimization algorithms to locat e st able struct ures. •Vibrat ion al frequency calculations to find the normal vibrat ional mo des of an opt imized struct ure . The vibrat ional spect rum can be displayed and the vibrat ional mot ions associat ed wit h specific t ransit ion s can be animated (17). 3- Computional Methods a-S emi- empirical Quantum Mechani cs HyperChem offers t en semi- empirical mo lecular orbita met hods, wit h opt ion s for organic an d main gro up co mp ounds, for t ran sition met al co mp lexes and spect ral simulation (18 ). P M3 were used fo r t he calculat ion of heat of fo rmat ion an d binding energy fo r all met al co mp lexes except platinum (IV) and vanadium (IV) comp lexes. b- Mole cular Mechani cs It has t hr ee im po rt ant co ncept s. Funct ion al for m , at om s t ypes and parameter sets. Each molecular mechanics met hod has it s own funct ion al form (Assisted Model Building and Energy Refinement ) (AMBER) is based on a fo rce field (19) . AMBER was used for t he calculat ion of t he binding energy and heat of fo rmat ion of plat inum(IV) and vanadium(IV) comp lexes. Re sult and Discussion A- Elemental Anal yse s T he import ance o f pr eparin g a new Schiff base arises fr om t heir virility as st art ing met erials for t he syn t hesis of many co mp lexes especially wit h t ran sition met al ions. T he p hysical and analy t ical data o f t he ligand and met al co mp lexes are given in t able (1). T he result s obt ained from metal analysis are in a satisfact or y agreem ent wit h t he calculated values .T he suggested molecular formula was also suppo rt ed by spect ral measurem ent as well as magnet ic moment s . B- Infrared S pectroscopic S tudy 1- T here is no appr eciable change t hat t oo k place in t he absorpt ion of νs(COC)and νas(COC) mo des in t he mo no meric zinc, palladium and cobalt co mp lexes, which ex clude t he possibility oxygen at om of met ho xy group part icipat ion in co or dinat ion . Furt herm ore , t here is a change in frequency an d int ensity of νC = N an d νN – N bands, t his behaviour refers t o co or dinat e modes of the ligand t hro ugh nit ro gen of isom et hane group and nit ro gen of t he t hio diazole ring (20) ,t able (2). 2- T he ligand behaviour is a different co or dinat e, i.e. t hr ough ox ygen o f met ho xy group and nit ro gen o f isomet han as a bridge for t he dimeric iron , plat inum, cupp er and van adium complexes or t hr ough sulfur at om of t hio diazale fo r t he nickel co mp lex . T he o t her behaviour of the ligand t oo k place as abident at e t hr ough N,N or N,S at oms fo r t he comp lexes cupper, vanadium , plat inum and nickel ion, while t he ligand behaves as a mo no det at e co ordinat e t hr ough nitrogen of isomet hane only in iron co mp lex (20 ). 3- νV = O stret ching mo de in vanadium comp lex was observed at 979 cm -1 as a stro ng band. Coordinat ion of sulfat e ion t his com plex was a bserved as a bident at e behavio ur (2 1). 4- T hese absor pt ion s were furt her suppor t ed by t he ap pearance frequencies of νM-S νM-O νM-N and νM-Cl respect ivly (20 , 2 2). 5- A brao d band was observed aro und (3 45 0-3 510) cm-1 in t he spect ra of t he comp lexes , assigned to a νO-H and suggest ed the presence o f wat er or et hanol molecules in t he crystal lattic of t he co mp lexes (2 3) . IBN AL- HAITHAM J. FO R PURE & APPL. SC I VO L.22 (3) 2009 C-Electroni c S pectroscopy S tudy 1-CuL Comple x T he elect ro nic spect ra of cupper comp lex sho wed on e broad absorpt ion band in t he region around 1298 7 cm -1 which was at t ribut ed to 2 B1g → 2 A1g t ran sition t able (3). T he position of this band is in an agreement wit h what is rep ort ed fo r highly distort ion oct ahedral geomet ry (2 4,25) . T he elect ro nic spect ra coupled wit h magnet ic mom ent (1.03 BM) studies indicat e squar planner geometric aro und Cu(II) comp lex (2 6) ,co nductivit y measurem ent showed t hat t he comp lex was ion ic.T he struct ure of t his comp lex can be suggest ed 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 Comple x T he blue – greenish cobalt (II) comp lex wit h ligand showed a magnet ic mo ment of (4 .8BM), which indicat es a h igh – spin t ype co mp lex . Elect ro nic spect rum in et hanol solution ex hibited a split band in t he range of (17 00 0- 14 00 0) cm -1 , t he split band is a t ypical t et rah edral spectra type and can be assigned as 4 A2→ 4 T 1(p) (ν3) , and in addit ion t here is a band at 3409 cm -1 which was t aking fro m IR and can be assigned to 4 A2→ 4 T 2(F) (ν2) t ran sition (27, 28) . T he co lour as well as t he magnetic moment furt her indicat ed tet rah edral geomet ry . T he (ν2) and various ligand field paramet er were calculated by reference t o T anaba- Sugano diagram for d 7 co nf igurat io t able (3).T he calculat ion of t he spin – orbit coupling const ant (x ) was µob s = µs. o -1 5.59 λ \ / 1 0 Dq weher µobs = T he o bserv ed effect ive magnet ic µs. o = T he elect ro nic spin only magnet ic mom ent T he resulting value (λ \ = -2 18.5 cm -1 ) ,t his value shows t he pr esent comp lex t o be distor t ed t et rah edral (29 ).T he nephelauxet ic fact or β was calculat ed and found t o be (0.63) indicat ing high degree of covalence in t he bon ding of ligand- donor at oms wit h cobalt (II) ion . T he molar conductance showed that t he co mp lex is elect ro lyt e, and t he following st ruct ural may be pro posed. IBN AL- HAITHAM J . FO R PURE & APPL. SC I VO L.22 (3) 2009 C o N N S N N 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-Ni L Comple x T he elect ro nic spect ral dat a , and t heir assignment as well as t he calculated ligand field paramet ers fo r nickel t hiodaizal benzyliden , are shown in t able (3 ). Considerin g t hese dat a and comp arisom wit h a large number of published work s (3 0- 32 ), led t o t he p ro posal of t he fo llowing dimeric struct ure. 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 st at isfies t he EAN co nf igurat ion for Ni . T he ligand field paramet ers B / ,β an d 10Dq, were calculated by fit t ing t he rat io of t he o bserved two bands, i.e ν2 and ν3 t o T -S. diagram as shown in d 8 configurat ion . T he calculation of spin- orbit co upling constant λ was µobs=µs.o( 1- 4λ \ 10Dq ) 3.35= 2.83 (1- �λ \ ����� ) T he result ing value = -318 6.3 cm -1 , shows t he present nickel co mp lex t o be tet ragonal distortion (3 3) or t his v alue is well sho wing t et ragon al dist ort ion .T he magnet ic measurem ent is (3.35BM), which shows t he comp lex t o be param agnet ic and conductivity studied show t hat t he comp lex is elect ro lyt e. IBN AL- HAITHAM J. FO R PURE & APPL. SC I VO L.22 (3) 2009 4-PtL Comple x T he elect ro nic spect rum of t he p lat inum (IV) shows t hree bands , t he first weak on ap peared at 1331 5cm -1 can be assigned to t he forbidden t ran sition 1 A1g → 3 T 1g an d ot her t wo bands wit h higher int ensity can be assigned t o t he follo wing t ran sition in oct ahedral en virom neut (34 ). 1 A1g → 1 T 1g 1 A1g → 1 T 2g T his coor dinat ion t yp e is comm on fo r P t (IV) comp lexes (3 3,34) , t he st udy of conductivit y behaviour in DMF shows t he co mp lex t o be ion ic . T he magnet ic measurem ent data is (0.82 BM) which shows t he comp lex t o be diamagnet ic, t able (3 ), t herefo re, t he fo llowing struct ure 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 Comple x Vanadium comp lex showed t wo bands relat ed t o squar py ram ide vanadium comp lex (3 4,35) . T hey were observ ed at 12 75 5, 17 699 cm -1 t able (3 ) fo r t he first and secon d t ran sition and were assigend to 2 B2g→ 2 Eg and 2 B2g→ 2 B1g tran sition respect ively (2 7,29,26,34). T he magnet ic moment (1 .3 BM) is lower t han spin only value, t his is due t o spin- couplin g (29, 36). Con duct ivit y in DMF showed t hat t he comp lex was ion ic, According t o t his ,t he fo llowing struct ural fo rmula 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 Comple x T he p rep ared co mp lex is colourless and diamagnet ic which is expect ed for d 10 ion . T he UV-Vis spect rum of t he co mp ound sho ws arelat ive ch ange in t he band posit ion co mp ared t o t hat of the free .T he conduct ivit y measurem ent fo r t his comp lex in DMF at 25°C showed t o be no nconduct ing (2 2µs.cm -1 ).T he most pro pable st ruct ral of t his comp lex is t et rah edral 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 N N 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 Comple x T he magnet ic measurem ent shows t he iron ion in it s or ange comp lex t o be ahigh spin paramagnet ic (5.32 BM), of d 5 co nf igurat ion T his suggestion was supp ort ed by t he number of maxima observed in t he elect ro nic spect rum of t he co mp lex , which sho w t wo maxima bands which may be assigned to t ran sition 6 A1g→ 4 T 2g(G), 6 A1g→ 4 A1g+ 4 Eg(G) as shown in t able (3) (3 3,37). The ν1 and racah paramet er β., and t he v alue of 10 Dq, which were calculat ed by reference t o T anab- Sugamo for d 5 configurat ion . T he conductivit y measurem ent in DMF show t he comp lex t o be no n- elect ro lyt e. Depending on t his infor mat ion , t he following st ruct ural may be p ro posed. Fe Fe ONO 2 ONO 2 ONO 2 ONO 2 ONO2 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 Comple x T he brown palladium comp lex shows stro ng ch arge t ran sfer bands which was ext ended t o t he visible region , so t he ligand field bands could not be est abished easily . Nev ert hless t wo weak bands at 224 71 an d 28169 cm -1 t able (3) may be assigned to t he t ran sition 1 A1g→ 1 B1g ( 2 a1g→ 1 a1g. 1 b1g) and 1 A1g→ 1 Eg ( 4 eg. 2 a1g→ 3 eg. 2 a1g→ 3 eg. 2 a1g. 1 b1g) respect ively, fo r spin- paired d 8 squar planner conf igurat ion wit h magnet ic mo ment value of (0 .00 BM). T his assignment was made by referen ce t o know palladium comp lex wit h squar planner stero chemistry , and came in a good agreem ent wit h published data (34 ,33). Con ductivit y value confirmed t he ionic struct ure . Depending on t his finding t he fo llowing struct ural fo rmula of t his comp lex may be pro po sed. IBN AL- HAITHAM J . FO R PURE & APPL. SC I VO L.22 (3) 2009 R N =C - RN N S Pd C l2 . 4 C 2 H 5 OH N N N S R - C R R= C 6 H 4 O C H 3 R= C 6 H 4 N (C H 3 ) 2 = H H D- S oluti on S tudy Molar rat io met ho d was fo llowed t o detemined t he M : L rat io . T he result of comp lexes in et hanol solut ion , suggest t hat t he met al t o ligand rat io was (1 : 2) , which are dimeric in nat ure fo r t he (cupp er, plat inum, nickel ), and mo nemer fo r palladium and cobalt comp lexes , and (1 : 1.7) fo r vanadium comp lex, while (1 : 1 ) fo r t he zinc an d iron met al co mp lexes , which were co mp arable to t hese obt ained from isolat ed solid st udy, t able (1). E- The oreti cal S tudie s (i) T he program HyperChem-6 was used for the semi- emp irical and molecular mechanic calculat ions, at opt imized geometr ies energies, the result on P M3 an d AMBER metho ds of calculat ion in gas phase fo r t he heat of formant ion (∆H ° ƒ) and binding energy (∆Eb) for t he ligands and their complexes were calculated and t abulat ed in table (4). Also P M3 was used for the ev alut ion of t he vibrat ional spect ra o f t he AM and Schiff base t o compare the theoretically calculat ed wave n umbers wit h the experimental values. T heor et ically calculat ed wave n umbers for t hese ligands sho wed that some deviat ions from the experimental values, t hese deviat ions are generally acceptable in theoret ical calculations and are described in t able(2) and (5 ) an d t he figs.(1) (2). (ii) Electrostatic Potential (E.P.):- Electron distribut ion governs the elect rost ic pot ent ial of mo lecules an d describes t he int eract ion of energy of the molecular syst em with a post ive point charge, so it is usef ul fo r finding sites of react ion in a mo lecule posit ive charged species t end to att ack a mo lecule where t he E.P. is strongly negat ive elect rophilic attack (38 ,39). (E.P.) of free ligand wa s calculated and plott ed as 2D co nt our to invest igat e t he reactiv e sit es of the mo lecules Fig(3), and one can int erpr et t he stereochemistry and rat es of many react ion s involv ing soft electrophiles and nuclephiles in term s of t he propert ies of frontier orbit als(HOMO an d LUMO). Overlap bet ween t he HOMO and LUMO is a govering factor in many react ions. T he HOMO and LUMO values were plott ed as 2D contour to get mo re informat ion about t hese molecules. T he result s of calculat ion showed that t he LUMO of transit ion metal ion prefer t o react wit h t he HOMO of sulfur an d nit ro gen atoms of Schiff base ligand. (iii) Optimized Geome tries Ene rgy of Metal Complexes for S chiff Base All t heoretically probable struct ures of metal complexes wit h schiff base were calculated t o search for t he most pro bable model building stable structure , these shapes fig.(4 ), show the calculated opt ima geometries for (L) and t heir metal complexes. The results of PM3 method of calculation in gas ph ase for the binding energies and heat of for mat ion of Co(II), Cu(II), P d(II), Zn(II), Ni(II) and Fe(III) , while AMBER met hod was used to calculate t he binding energies which is equal t o heat formation for both Pt(IV) and V(IV) comp lexes , an d are described in table (4). IBN AL- HAITHAM J. FO R PURE & APPL. SC I VO L.22 (3) 2009 References 1. T ai,X.; Yin, X.; Chen, Q. and T an,M. (2003 ). 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Deshm uke ,K. and Bho be, R. A. (1979)J. Inor g. Nucl. Chem. ,40, 134. 33. Jorgeuson, C. K. (1968)."Absorpt ion Spect ra and Chemical bonding in Complexes"; pergaman press. 34. Figgis, B., N.,(1966). "Introduction to Ligand Field"; Int erscience; 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 ). "Comp rehensive Inorganic Chemistry", P erganmon Press. 38. St eword,J .J .P .; MOP AC 2000 VIO fo r windows ( Singie), MO20-AS-W , Fujit su ST EM EUROP E. 39. Anderson,W .P .; Behm, P. and Glennon,T .M. , (1997).J .P hys. Chem.,vol. (101) IBN AL- HAITHAM J . FO R PURE & APPL. SC I VO L.22 (3) 2009 d : decompose d poin O A C =C H 3- C -O = O Table (1): Physical data for the ligand (L) and their metal complexes Suggest Mole cular formula Metal to ligand ratio Atomi c Abs. Found (Cal .) Yiel d % m.p C° Col our Co mp. C18 H18 N4 S O ــــــ 114 84.0 ــ Pale Orang L [Cu2(L)4](NO 3)4. C2H5OH 1 : 2 5.58 (6.70) 50.0 84 Pale Brown Cu L [Co(L)2](NO 3)2.3 C2H5OH 1 : 2 5.29 (4.51) 75.8 63 d Bluish- Green Co L [Ni 2(L)2]2(NO 3)4. H2O 1 : 2 6.78 (7.39) 51.7 160 Dark Orang Ni L [Pt(L)2Cl 2]2Cl 4.4 C2H5OH 1:2 17.61 (17.88 ) 40.0 204 Dark Orang Pt L [(VO)2(L)3S O4]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(NO 3)3]2.2 H2O 1:1 .96 (5.90) 64.0 65 Reddis h- orang Fe L [Pd( L)2]Cl 2.4C2H 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 Freque ncies of AM Fig. (2) The Cal culated Vibrational Freque ncies of S chiff 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=Ni so (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 Electrostati c Potential as 2D Contours for L Fig. (4): Conformational Structure of AM, L and their Complexes Electrosta tic 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) : Electroni c 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 4 A2 → 4 T2(F) 4 A2 → 4 T1(F) 4 A2 → 4 T1(P) 11 28 718 .3 0.5 0. 63 3663 .3 107 74.5 4. 8 18 2 Cu L 12987 2 B1g → 2 A1g 1. 03 21 V L 12755 17699 2 B2g → 2 Eg 2 B2g → 2 B1g 1. 3 18 2 Pt L 13315 23148 27397 1 A1g → 3 T1g 1 A1g → 1 T1g 1 A1g → 1 T1g 0. 82 20 5 Ni L 13850 1067.2 18148 23529 (26250 )cal. 3 A2g → 1 Eg 3 A2g → 3 T2g(F) 3 A2g → 3 T1g(F) 3 A2g → 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 6 A1g→ 4 T1g(G ) 6 A1g→ 4 T2g(G ) 6 A1g→ 4 T1g+ 4 Eg 13 00 677 .8 1.7 0. 52 1152 0 101 67 5. 32 21 Pd L 22471 28169 1 A1g → 1 B1g 1 A1g → 1 E1g 0. 00 69 Table (2) The most diagnosti c FT- IR ban ds 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 Ene rgetic (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 Ni L -18212.6603680 315.9996320- CuL 469.320923 PtL -377002.125000 VL -5884.83965 -27.446653 Zn L -9122.034 151.5953 PdL W h er e : * : E x p er im en ta l fr eq u en cy * * : T h o re ti ca l fr eq u en cy * * * : E rr o r % d u e to m ai n d if fe re n ce i n y h e ex p er im en ta l m ea su re m en ts a n d t h eo re ti ca l tr ea tm en t o f v ib ra ti o n al s p e ct ru m . ( 1 3 2 8 2 )* * - υ A r- N T a b le ( 5 ): C o m p a ri so n o f ex p er im en ta l a n d th eo re ti ca l v ib ra ti o n a l fr eq u en ci es (2 9 7 0 ,2 8 9 4 )* * 1 0 3 5 ) (1 2 8 1 , 1 0 0 3 .6 )* * (- 2 . 3 ,- υ O C H (1 3 2 5 2 )* * * ) (1 3 3 0 )* * (4 . 6 υ N C N (7 1 7 . 3 )* * * (8 3 9 ) * * ( - 8 υ C = S (1 1 5 5 . 7 )* * ) (1 1 6 6 )* * (0 υ C S C (1 4 3 9 5 )* * * ) (1 4 4 1 )* * (1 υ N - N (1 0 7 3 .6 , 1 1 6 6 .1 )* * 1 1 2 2 ) (1 2 3 8 .0 1 , 1 0 1 4 .6 )* * (- 9 . 0 , 9 υ N C S (1 6 2 8 . 6 ) * * - υ C = N is - 3 1 7 2 ) (3 5 3 4 , 3 4 2 6 )* * ( -7 . 0 , 8 υ N H 2 L 1 A M S y m b . یثم ابن مجلة لوم الھ صرفة للع لتطبیقیة ال 20 )3( 22المجلد وا 09 – 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 ،)III(والحدیــد ،)II(والزنــك ،IV)(والبالتـین ،)II( والبالدیــوم ،)II(والنیكـل ،)II(ات النحــاسثایودیـازول ومعقداتــه مـع االیونــ شــخص وعــین الشــكل الهندســي للمركبــات المحضــرة بأســتخدام األجهــزه الطیفیــه ، األشــعة IV (0(والفنــادیوم،) II(والكوبلـت درس 0قیـاس الحساسـیة المغناطیسـة والتوصـیل الكهربـائي لهــا ال عـنضــفالمرئیـة –تحـت الحمـراء واألشـعة فـوق البنفسـجیة مقاربة مع النتائج التي تم الحصـول علیهـا ااعطت نتائجاذ ،حالیل بأتباع طریقة النسب المولیةطبیعة المعقد المتكون في الم .لة الصلبة المعزولةابالح Hy(اجریت معالجة تكوین المعقدات نظریـًا فـي الطـور الغـازي باسـتخدام برنـامج p erChem-6 ( بتطبیـق المیكانیـك PMالجزیئـي والشـبه التجریبــي فـي الحســاب وذلـك باسـتخدام الــدوال 3 ،AM BER لحسـاب حــرارة التكـوین(∆Hƒ ° وطاقــة ( ، كــذلك حســب الجهــد األلكتروســتاتیكي لبیــان المواقــع .كلفــن للیكانــد ومعقداتــه المحضــرة 298وبدرجــة حــرارة ) Eb∆(التــرابط PMریـًا وبأسـتخدام الدالـة لتــردد األهتـزازي نظشـف وجـرى حسـاب ا الفعالـة لقاعـدة لقاعــدة شـف ومقارنتهـا مـع القـیم المقاســه 3 ووجــد أن هنـاك توافقــًا اقیاسـی اثایودیـازول مركبــ – 4، 3، 1 –) بــارا میثوكسـي فینیــل ( 5 –امینـو -2عملیـًا بأســتخدام 0كبیرًا بین القیم العملیة والمحسوبة نظریًا مع زیادة امكانیة تشخیص الحزم بشكل ادق