Chemistry - 294 مجلة إبن الهيثم للعلوم الصرفة و التطبيقية 2012 السنة 25 المجلد 3 العدد Ibn Al-Haitham Journal for Pure and Applied Science No. 3 Vol. 25 Year 2012 Synthesis and Characterization of Some mixed-Ligand Complexes Containing N-acetyl Tryptophan and (2, 2′-bipyridine) with Some Metal Salts B. M. Sarhan, T.A. Hamdan ،B. Z. Naema Department of Chemistry, Education College Ibn- Al-Haitham, University of Baghdad *Teacher Training Institutes, Ministry of Education Received in : 15 February Accepted in : 17June 2012 Abstract Some metal ions (Mn+2, Fe+2 ,Co+2,Ni+2 ,Cu+2, Cd+2 and Hg+2) complexes of N-acetyl Tryptophan( AcetrpH) and (2, 2′-bipyridine) (2, 2′-Bipy)have been synthesized and then characterized on the basis of their FT-IR, UV-Vis spectroscopy, magneticsuscptibity conductivity measurements and atomic absorption;from the results obtained and the propsed molecular structure for these complexes as octahedral geometry,the following general formula has been given for the prepared complexes. [M+n(Acetrp)2(2, 2′-Bipy)]. Where M= Mn+2, Fe+2 ,Co+2,Ni+2 ,Cu+2, Cd+2 ,Hg+2 (Acetrp)- =Ligand ion(N-acetyl Tryptophan) (2, 2′-Bipy) = 2,2′-bipyridine Key word: N-acetyl tryptophan, 2,2′-bipyridine, complexes. Introduction Complexes of amino acids present important pharmacological interest as several of them show a wide spectrum of effects, including anti-inflammatory, antiulcer, anti convulsant and even anti-tumoral activity [1-5]α-amino acids form stable five –member chelate complexes with transition metal ions and this complexation has found an application in selective complexing agents based on amino carbon acids[6].Some transition metal complexes of N- acetyl Tryptophan have been synthesized and characterized[7]and synthesis and characterized complexes of Fe(II) and U (III) with2, 2′-bipyridine[8,9] also mixed ligand complexes of Zn(II) and Cd(II) containing ceftriaxone and amino acids as glycine, proline and methionin have been synthesized and characterized[10].We have invistigated in this paper,the preparation and properties of some metal ion complexes with N-acetyl Tryptophan and amine adduct 2,2′-bipyridine. Experimental Materials and measurements Metals salt (MnCl2.4H2O, FeSO4.7H2O, CoCl2.6H2O, NiCl2.6H2O, CuCl2.2H2O, CdCl2.H2O and HgCl2) were obtained from Fluka,Merk in high purity while Ligand (N-acetyl Tryptophan) and(2,2′-bipyridine)were obtained form (B.D.H.). Conductivity measuremeants were carried out using philips PW.Digital- meter .The FTIR spectra in the region(4000-200)cm-1 were recorded using (shimadzu,FTIR-8300).Infrared spectrophotometer as cesium-iodid disc. The uv-vis. specrtra were recorded using (shimadzu uv-vis 160A), uv-vis spectrophotometer in dimethylform amide solution(10-3),metal contents Chemistry - 295 مجلة إبن الهيثم للعلوم الصرفة و التطبيقية 2012 السنة 25 المجلد 3 العدد Ibn Al-Haitham Journal for Pure and Applied Science No. 3 Vol. 25 Year 2012 of the complexes were determined by Atomic absorption technique using (shimadzu AA6806),Atomic absorption spectrophotometer the magnetic moments (µeff.B.M.) were calculated on Farday method by using(magnetic susecptipility balance) model MSB-MKT measurements carrietedout at college of science ALnahrain university melting point were determined using stuart-melting point apparatus. General method for the synthesis a) N-acetyl Tryptophan( AcetrpH) was derprotenated according to following reaction: N C H C H C O O H NH C O CH3 H + KOH N C H2C H C O O K NH C O CH3 + H2O Ethanol 1 Syn thesis of complexes : An aqueous solution of metal salt (0.5g)(2mmole)of the ligand(Actrp- )dissolved in (20 ml) of ethanol containing(0.12g)(2mmole) of KOH,solution of (1mmole) metal salt contains(0.198g, 0.28g, 0.24g, 0.24g, 0.17g, 0.14g, 0.20g and 0.27g) of MnCl2 .4H2O, FeSO4.7H2O, CoCl2.6H2O, NiCl2.6H2O, CuCl22H2O, ZnCl2, CdCl2.H2O and HgCl2)respectivel in ethanol was added drop wise to mixture. The mixture was stirred for an hour at room temperature,complexes were separated by adding solution of the (2,2′-Bipy) (0.16g,1mmole) in ethanol and by treating the solution with diethylether until complete precipitation. The precipitation were crystallized form ethanol and dried at(50ºC). Result and discussion The isolated complexes were crystalline solids soluble in some of common solvents such as dimethylformamide (DMF),dimethyl sulphoxide (DMSO) they are relatively thermally stable. The conductivity measurements in DMF indicated the non-electrolyte their behavior, table(1) includes the physical properties the analytical data confirmed the (1:2:1)(metal:(Acetrp):( 2,2′-Bipy))composition of the complexes.The magnetic measurements(µeff B:M) for the complexes are also listed in table(1). Spectral studies Table (2) describes the important absorptions and assignments for the free ligands and its complexes. The spectrum of free ligands the infrared spectrum of ligand (AcetrpH) fig(2). Exhibited a strong band at(3360)cm-1 assigned to the υ(N- H),while another strong absorption band at (1720)cm-1 appeared could be explained as (OCO- )asym where the (OCO- )Sym was noticed at (1240) cm-1 [11-13]the spectrum of free (2, 2′-Bipy) showed band observed at (1581)cm-1 was assigned to υ (C=N) [14] . The spectra of complexes Exhibited a marked difference fig(3) the absorption band belonging to the stretching vibration of υ(N- H) of the amine group have been found in the range between(3400- 3450)cm-1 shifted to higher frequencies by (90-40)cm-1 suggesting the possibility of the coordination of ligand (Acetrp) through the nitrogen atom at amine group[15] .absorption assigned for (OCO- )Sym was noticed at the range (1415-1365)cm-1shifted to higher position by(125-175)cm-1 while the band caused by (OCO- )asym appeared between (1574-1650)cm-1 Chemistry - 296 مجلة إبن الهيثم للعلوم الصرفة و التطبيقية 2012 السنة 25 المجلد 3 العدد Ibn Al-Haitham Journal for Pure and Applied Science No. 3 Vol. 25 Year 2012 shifted to lower frequencies by (146-70)cm-1which indicates the coordination of the carboxylic group to metal ion[16-17] The stretching vibration band υ(C=N) has been found in the range(1550-1427)cm-1 shifted to lower frequency by (154-31)cm-1which means that the nitrogen atom of (2, 2′-Bipy) was involved in the coordination[18] metal-nitrogen and metal-oxygen bands were further confirmed by the presence of the stretching vibration of υ(M-N)and υ(M-O) around (410- 655)cm-1and (308-472)cm-1 respectively. Electronic spectra Free ligands (AcetrpH) and (2, 2′-Bipy) bands of maximum absorptions and assignments related to the ligands its complexes are listed in table(3).The ligand fig(3) exhibited an absorption band in(UV) region at wave number(33500)cm-1which may be attributed to(π→π*) transition. Other band of low intensity appeared at(25641)cm-1was expressed at the(n→π*),free(2, 2′-Bipy) showed absorption bands at(42553)cm-1 and (35461)cm-1which have been assigned as (π→π*) and (n→π*) transitions respectively[19]. -[Mn(Acetrp)2(2, 2′-bipy)] (d5) The yellow complex spectrum showed two absorption at(34013)cm-1and (27173)cm- 1which may be attributed to (CT)and [20] 6A1g→4T2g(D) transitions respectively .The observed magnetic moment value Mn(II) complexe is (5.76)B.M. which is the predicted high- spin value for an octahedral Mn(II) complex. -[Fe(Acetrp)2(2, 2′-bipy)] (d6) The spectrum of the red complex showed two absorptions have been noticed at (34013)cm-1and (14409)cm-1which may be attributed to (CT)and 5T2g→5Eg transitions respectively[21]the magnetic moment value (5.45)B.m for Fe(II) complex in the range of octahedral. -[Co(Acetrp)2 (2, 2′-bipy)] (d3) The spectrum of violet complex fig(4) exhibited the following bands at(33444)cm- 1(27397)cm-1,(13422)cm-1 and (10172)cm-1which have been assigned as (C.T.),4T1g →4T1g(p) , 4T1g→4A2g and 4T1g→4T2g respective and(B′) found to be (686.86) and β′ = comes out to be (0.71) [22]which indicates prence covalent band in the complex, and the magnetic moment value for Co(II) complex is (4.57) B.M confirmed the aforementioned geometry. -[Ni(Acetrp)2(2, 2′-bipy)] (d8) The spectrum of green complex exhibited the following absorptions at(34013)cm-1 (25641)cm-1 (17094)cm-1and(12626)cm-1which have been assigned as(C.T.) 3A2g→3T1g(p), 3A2g→3T1g(F) and 3A2g→3T2g respectively and(B′) found to be(323.8)cm-1 and β′= comes out to be (0.31) [23-24]which indicates dicates prence covalent band in the complex and the magneticmoment. -[Cu(Acetrp)2(2, 2′-bipy)] (d9) The spectrum of green complex gave two bands at (33444)cm-1and (15243)cm-1 which may be attributed to (C.T.) and 5Eg→2 T2g transitions respectively[25-26]and magnetic moment for Cu(II) complex is (1.78B.M confirmed the aforementioned geometry. -The white complexes[Zn(Acetrp)2(2, 2′-bipy)], [Cd(Acetrp)2(2, 2′-bipy)] and [Hg(Acetrp)2(2, 2′-bipy)] (d10) confirms the absence of any(d→d) transition[27-28] . According to spectral data as well as those obtained from elemental analyses, the chemical structure of the complexes may be suggested as octahederal for [M(Acetrp)2(2, 2′-bipy)] M+2 = ( Mn, Fe, Co, Ni, Cu, Cd, Hg) Acetrp=N-acetyl tryptophan 2, 2′-bipy= 2, 2′-bipyridine Chemistry - 297 مجلة إبن الهيثم للعلوم الصرفة و التطبيقية 2012 السنة 25 المجلد 3 العدد Ibn Al-Haitham Journal for Pure and Applied Science No. 3 Vol. 25 Year 2012 References 1. Sorenson, J.R.J. (1976) " Copper chelates as possible active forms of the antiarthritic agents" J. Med. Chem., 19: 135–148 2. Sorenson, J.R.J. (1982) "metal ions in Biological systems"M.Dekker, newyork:14:77- 124. 3. Baran, E.J. (1985) "Evaluation of Superoxide Dismutate-Like Activity in Some Copper(II) Complexes of Aminoacids ",Acta Farm.Bonaerense 4 :125-23 4. Farrel, N.(1989) "transition metal complexes as Drugs and chemo tberapeutic Agents " Kluwev, Dordrecht. 5. Atilio, I.; Anzellotti, M. S. and Nichotas, F. 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(1968) "Electronic spectra of transition metalcomplexes" McGraw-Hill publishing,company LTd. 22. Lever, A.B. (1968) "coordination Chem.ReV."pergament press oxford, London,3:119. 23. Jorgensen,C.K. (1963) "synthesis, characterization and anti bacterial activity of Mn(lI), Co(lI), Ni(lI) and Cu(lI) complexes of U-carboxaldelyda penyl hydrazone-1- phenyl-3-methyl-2-pyrazoline -5-one"Advan.chem. phys,5(33):22. 24. Juran, N.;Periesiuk ,B.; Monojloricl, niktic ,S.R.; and Cleap, M.B. (1990) " Nitrogen- 15 NMR coordination shifts of β-alanine and glycine in cobalt(III) complexes".Inorg.chem;29:1491-1495. 25. AL-Hashimi, S.M.; Sarhan, B.M. and Alwan, A. Y. (2005) "synthesis and characterization of same mixed- ligand complexes contananing -N- acetyl Glycine and pyridine with some metal ions" Ibn-AlHaitham J. for pure and appl.sci.(4)18. 26. Walton, R. (1967)" Synthesis and dynamic NMR studies of fluxionality in palladium(II) and platinum(II) complexes of 2,4,6,-tris(2-pyridyl)-1,3,5-triazine (TPT) and 2,4,6-tris(2-pyridyl)-pyrimidine (TPP);Inorg. Chem. 10: 257-268. 27. G.marcotrigiano,L.; Menabu, P. and Saladini, M. (1979),"structures of bis(U- amino pyridinium)tetrachloro cuprate(II) mono hydrate"Inorganic chimica Acta. 32:149-155 28. Huheey, J.E. (1983) "Inorganic chemistry, principles of structure and Reactivity"3rd Edition, Harper International SI Edition; Maryland. Chemistry - 299 مجلة إبن الهيثم للعلوم الصرفة و التطبيقية 2012 السنة 25 المجلد 3 العدد Ibn Al-Haitham Journal for Pure and Applied Science No. 3 Vol. 25 Year 2012 Table (1) physical properties of the complexes Complexes Color Dec.ºC Or M.P. M% Calculate (Found) Molar conductivity (ohm-1.cm-2mol-1) In DMF 10-3M Meff (B.M.) AcetrpH(ligand) White 206-204ºc 1 2, 2′-bipy(ligand) White 73-70ºc 2 [Mn(Acetrp)2(2, 2′-bipy)] Yellow 220ºd 7.82 (6.85) 3 5.76 [Fe(Acetrp)2(2, 2′-bipy)] Red 225ºd 7.94 (8.68) 3 5.45 [Co(Acetrp)2(2, 2′-bipy)] Violet 226ºd 8.35 (7.87) 8 4.57 [Ni(Acetrp)2(2, 2′-bipy)] Green 210ºd 8.32 (8.01) 9 3.25 [Cu(Acetrp)2(2, 2′-bipy)] Green 180ºd 8.94 (7.52) 3 1.78 [Zn(Acetrp)2(2, 2′-bipy)] White 224ºd 9.18 (8.26) 4 0 [Cd(Acetrp)2(2, 2′-bipy)] White 296ºd 14.8 (13.72) 3 0 [Hg(Acetrp)2(2, 2′-bipy)] White 234ºd 23.67 (22.89) 3 0 Table (2) the characteristic infrared of (AcetrpH),( 2, 2′-bipy) and its metal complexes Complexes υ(C=N) (2,2'- Bipy) υ(NH:) υ(COO-)asy υ(OCO-)Sym υ(M-N) υ(M- O) AcetrpH (Ligand) 3360 1720(S) 1240 2,2'-Bipy( Ligand) 1581 [Mn(Acetrp)2(2,2'-Bipy)] 1550(w) 3450(b) 1600(s) 1410(w) 410(v.w.) 370(w) [Fe(Acetrp)2(2,2'-Bipy)] 1427(s) 3402(b.) 1604(m) 1365(w) 563(m) 324(m) [Co(Acetrp)2(2,2'-Bipy)] 1450(m) 3400(sh,) 1620(s) 1401(m) 486 472 [Ni(Acetrp)2(2,2'-Bipy)] 1490(w) 3409(b) 1650(b) 1404(b) 655 378 [Cu(Acetrp)2(2,2'-Bipy)] 1490(w) 3410(b) 1574(b) 1405(m) 578 425 [Zn(Acetrp)2(2,2'-Bipy)] 1442(m) 3409(b) 1604(s) 1396(m) 563 424, [Cd(Acetrp)2(2,2'-Bipy)] 1490(w) 3410(b) 1610(s) 1410(s) 410(w) 308 [Hg(Acetrp)2(2,2'Bipy)] 1525(v.w,) 3410(b) 1610(s) 1415(s) 610(w) 401 S=strong, b= broad, m= middle, w= weak, s.b.= strong brod Chemistry - 300 مجلة إبن الهيثم للعلوم الصرفة و التطبيقية 2012 السنة 25 المجلد 3 العدد Ibn Al-Haitham Journal for Pure and Applied Science No. 3 Vol. 25 Year 2012 Table(3) :The electronic spectra for the free ligand (AcetrpH),( 2, 2′-bipy) and its complexes in DMF(10-3)M Complexes גmax(nm) Wave number (cm-1) Є max L.mo1-1.cm-1 Remarks AcetrpH (Ligand) 298.5 390 33500 25641 2439 13 *π→π n→π* 2,2'-Bipy( Ligand) 235 282 42553 35461 2950 3675 *π→π n→π* [Mn(Acetrp)2(2,2'-Bipy)] 294 368 34013 27173 1983 351 C.T. 6A1g→4T2g(D) [Fe(Acetrp)2(2,2'-Bipy)] 294 694 34013 14409 1858 5 C.T. 5T2g→5Eg [Co(Acetrp)2(2,2'-Bipy)] 299 365 745 983 33444 27397 13422 10172 2312 774 12 11 C.T. 4T1g→4T1 g (P) 4T1g→4A2 g (F) 4T1g→4T2 g (F) [Ni(Acetrp)2(2,2'-Bipy)] 294 390 585 792 34013 25641 17094 12626 1819 89 50 12 C.T. 3A2g→3T1 g (P) 3A2g→3T1 g (F) 3A2g→3T2 g (F) [Cu(Acetrp)2(2,2'-Bipy)] 299 656 33444 15243 2254 107 C.T. 2Eg→2T2g [Zn(Acetrp)2(2,2'-Bipy)] 294 34013 1794 C.T. [Cd(Acetrp)2(2,2'-Bipy)] 297 33670 1545 C.T. [Hg(Acetrp)2(2,2'Bipy)] 294 34013 1858 C.T. Fig.(1):General structure of complexes N O O M N N N Acetrp A ce tr p Chemistry - 301 مجلة إبن الهيثم للعلوم الصرفة و التطبيقية 2012 السنة 25 المجلد 3 العدد Ibn Al-Haitham Journal for Pure and Applied Science No. 3 Vol. 25 Year 2012 Fig.( 2):FT-IR spectrum of Ligand Fig.(3) :FT-IR spectrum of [Zn(acertp)2(2,2′-bipy)] Chemistry - 302 مجلة إبن الهيثم للعلوم الصرفة و التطبيقية 2012 السنة 25 المجلد 3 العدد Ibn Al-Haitham Journal for Pure and Applied Science No. 3 Vol. 25 Year 2012 Fig.(4):uv-vis spectrum of Ligand N-acetyl tryptophan Fig.(5): uv-vis spectrum of Complex [Co(acetrp)2(2, 2′-bipy)] Chemistry - 303 مجلة إبن الهيثم للعلوم الصرفة و التطبيقية 2012 السنة 25 المجلد 3 العدد Ibn Al-Haitham Journal for Pure and Applied Science No. 3 Vol. 25 Year 2012 N –تحضير وتشخيص بعض المعقدات الفلزية مع ليكاندات مختلطة من 2,2'Bipyridin تربتوفان و استيل ن نعمةتقي الدين حمدان ، *بان زيدا باسمة محسن سرحان، جامعة بغداد ,ابن الهيثم -كلية التربية ,قسم الكيمياء **معهد اعداد المعلمات / وزارة التربية 2012حزيران 17قبل البحث في: 2012شباط 15استلم البحث في : الخالصـــــــــة Bipy'2,2فان واستيل تربتو-Nبعض المعقدات الفلزية التي تحتوي على ليكاندات مختلطة للمشتق توشخصت حضر والتوصيلية الموالرية ،واالشعة فوق البنفسجية ) ،هذه المعقدات بالطرائق الطيفية(االشعة تحت الحمراء ت،وقد درس ومن نتائج هذه الدراسات التشخيصية اقترح شكل ثماني .والخاصية المغناطيسية وحساب النسبة المئوية للفلز في المعقد ، تي :يأامما تم التوصل الى الصيغه العامة للمعقدات وكالسطوح للمعقدات المحضرة ك [M+n(Acetrp)2(2, 2′-Bipy)]. Hg+2 , Cd+2, Cu+2, Ni+2 , Co+2, Fe+2 , Mn+2=M اذ (N-acetyl Tryptophan) الليكاند االيوني = (Acetrp)- 2,2′-bipyridine = (2, 2′-Bipy) داي برديل ، المعقدات . -2,′2تربتوفان ، استيل -N: ةالكلمات المفتاحي