` @1a@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹26@@ÖÜ»€a@I1@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (1) 2013 Synthesis And Characterization Of New Metals Complexes Of [N-(acetyl amino) Thioxomethyl] Valine Alia S. Kindeel Dept. of Chemistry/College of Education For Pure Science(Ibn Al- Haitham)/ University of Baghdad Received in : 6 May 2012 , Accepted in : 22 October 2012 Abstract A new ligand [N-(acetyl amino) thioxomethyl] valine was prepared from the reaction of acetyl iso thiocyanate with valine. The ligand was characterized by FT-IR, UV- vis and 1HNMR spectrum, The complexes with some metal ions (M +2 =Co,Ni,Cu,Zn,Cd,Hg) have been prepared and characterized. The structural diagnosis were established by IR,UV-Vis spectrum, flame atomic absorption spectroscopy conductivity and magnetic susceptibility ,the complexes showed tetrahedral geometry around the metal l. Keywords : valine, acetylisothiocynate complexes 225 | Chemistry ` @1a@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹26@@ÖÜ»€a@I1@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (1) 2013 Introduction Metal complexes of amino acids posses considerable potential in many application including biological,clinical,antibiotics and tumor inhibitors [1-4] ,metal complexes of Cu(II),Ni(II),Cr(III),and Fe(II) chloride with Schiff base ligand[5] derived from reaction between leucine and 2 – acetyl pyridine were prepared and Brij [6], used paper electro phoretic technique (PET) to calculate the stability constants of (Be(II) ) –proline and Co-proline Complexes, also Dhafir and co-work[7] had synthesis, characterization and biological activity of some complexes of some new amino acid derivatives with transition metals . This work includes preparation of some transition metals complexes of [N-(acetyl amino ) thioxomethyl] valine . Experimental All reagents used were analar or chemically pure grade by British drug house(BDH) ,Merk and Fluka. Metal salts (CoCl2.6H2O, NiCl2.6H2O, CuCl2.2H2O , ZnCl2, CdCl2.H2O, HgCl2), valine, ammoniumthiocyanate, acetyl chloride (CH3COCl) acetone 99% dimethyl formaminde 99.5% (DMF), ethanol 99% . Instruments HNMR were recorded using ultra shield 300MHz Switzerland, at university of AL-Al- bayt, Jordan. conductivity measurements were carried out using Philips pw digital meters conductivity in DMF at 10-3M .FT-IR spectra were recorded as KBr discs in the range (4000- 400) cm -1 using shimadzu FT-IR. UV-visible spectra were recorded by shimadzu UV-8300 vis-160 A , ultra violet spectra photometer, at the range of (200-1100) nm at 10-3 M in DMF. metal contents of the complexes were determined by atomic absorption using (shimadzu aa 6806) atomic absorption spectra photometer. magnetic susceptibility (µeff B.M) were recorded by farada method using balance magnetic susceptibility) model MsB –MKI). melting points were determined by using (shtutart –melting point apparatus). Synthesis of the ligand 1- Preparation of the acetyl -isothiocyanate : mixture of acetyl chloride (1.9 ml) (1mmole) and ammonium thiocynate (2gm)(1mmol) in 25 ml acetone was stirred under refluxed for 3 hours and then filtered , the filtrate was used for further reaction[8] 2- Preparation of [N-(acetyl- amino) thioxomethyl] valine [ATV]. 3.08 gm (1mmol) of valine in 20 ml acetone was rapidly added to the above solution to maintain vigoross reflux. After refluxing for 6 hours , the resulting solid was collected , washed with acetone and recrystallized from ethanol . Scheme (1) (yield 80%), (M.P. 1350 C). 226 | Chemistry ` @1a@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹26@@ÖÜ»€a@I1@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (1) 2013 Scheme (1) :preparation [N-(acetyl amino )- thioxo methyl] valine(ATV). Synthesis of the complexes 0.2 g (2mmol) of the ligand (ATV) was dissolved in 25 ml of ethanol containing 0.05g (2mmol) of KOH, Then the solution of (1mmol)metal salt (CoCl2.6H2O, ,NiCl2.6H2O, CuCl2.2H2O ,ZnCl2,CdCl2.H2O and HgCl2) (0.11g,0.11g,0.08g,0.06g,0.09g and 0.120g) respectively in ethanol was added drop-wise to the solution of the ligand(ATV), the precipitate formed immediately, after stirring the mixture at room temperature for 2 hours , the precipitate was collected by filtration, washed with ethanol and dried . Results and discussion The solid complexes,soluble in some commen solvents such as dimethylformamide , dimethylsulphoxide , and relatively thermally stable . The molar conductivity of all complexes in DMF was found to be non electrolyt . Table (1) includes the physical properties for the ligand and its complexes Spectral studies H1NMR spectrum for the ligand (ATV) The H1NMR (CDCL3) spectrum of (ATV) Fig.(1) showed the following signals : doublet (d) at δ(0.8-1.2)ppm for (6H,2CH3) , singlet(s) at δ(2.1)ppm for( 3H,CH3CO), multiplet(m) at δ(2.32-3.10) ppm for (1H,CH(CH3)2) , triplet (t) at δ(4.43-4.53) ppm for (1H,CHCOOH) , doublet (d) at δ (6.12- 6.15) ppm for (1H,NH ) , singlet (s) at δ(7.27) ppm for impurit of solvent (CDCl3) , singlet(s) at δ(9.12) ppm for (1H,NHsec.amide) , singlet(s) at δ(12.6) ppm for (1H,COOH). Infrared spectra FT-IR spectrum of the free ligand (ATV) Fig.(2) showed bands due to amide υ(NH) υ(C=0) and υ(C=S) which were observed at (3369) cm-1 (1602) cm-1 and (1217) cm-1 respectively While another absorption band appeared at (1728) cm-1 could be explained as υ(COO)asym [9-10] were the υ(OCO)sym was noticed at(1315) cm-1. 227 | Chemistry ` @1a@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹26@@ÖÜ»€a@I1@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (1) 2013 The FT-IR spectra of complexes These spectra exhibited a marked difference between bands Fig.(3) belonged to the stretching vibration of υ(N-H) of the amine group in the range between(3426-3383) cm- 1 shifted to higher frequencies by (93-14) cm-1 suggesting the possibility of the coordination of ligand[11-13] through the nitrogen atom at the amine group ,absorption assigned for υ(OCO)sym was noticed at the range (1388-1438) sym cm-1 shifted to higher frequencies by (123-73) cm-1 while the band caused by υ(COO)asym appeared between (1506-1629) cm- 1 shifted to lower frequencies by (89-222) cm-1 which indicates to the coordination of the carboxylic group to the central ion [12-14] . The stretching vibration band υ(C=O) and υ(C=S) carbonyl group either show no change or very little in their frequencies(1610-1600)cm-1 and (1220-1203)cm-1 respectively therefor indicating do not coordinate to the metal ions[15] Metal nitrogen and metal-oxygen bands were confirmed by the presence of the stretching vibration of υ(M-O) and υ(M-N) around(425-570)cm-1 and (401-426) cm-1 respectively . Table (2) describes the important bands and assignments for free ligand (ATV) and its complexes Electronic spectral The UV- visible of the ligand (ATV) and its complexes are recorded in table(3) . the solution of the ligand (ATV) in 10-3 M (DMF) exhibited two peaks Fig.(4) at (36496) cm- 1 and (30487) cm-1 which are attributed to Π Π* and n Π* transition respectively [16]. The spectra of complexes - [Co(ATV) 2] d7 : the spectrum of the deep-blue exhibited the following bands at (35211) cm-1 and (18656) cm-1 attributed to (C.T) and 4A2 4T1(p) respectively [17-18] - [Ni(ATV)2](d8) : the spectrum of green complex , gave two bands at (42016) cm-1 and (26881) cm-1 caused to (C.T) and 3T1( F) 3 T1(p) transition respectively .[19] - [Cu(ATV)2) d9 the deep green complex spectrum Fig. [5] showed two absorptions at (36363) cm-1 and (12062) cm-1 attributed to (C.T) and 2T2 2 E transitions receptively [20]. - the yellow complexes of [Zn(ATV)2)] , [Cd(ATV)2], [Hg(ATV)2] showed only charge transfer of (M L) in the range (38461-27322) cm-1 respectively [21] According to spectra data as well as those abtained from elemental analysis the chemical structure of the complexes may be suggested as [M(ATV)2] Were M= Co+2 , Ni+2 , Cu+2 , Zn+2 ,Cd+2 and Hg+2 ATV=[N-(methyl amino )-thioxomethyl ] valine 228 | Chemistry ` @1a@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹26@@ÖÜ»€a@I1@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (1) 2013 References 1. Sigle , H. (1979) Metal Ions in Biological Systems ,1st edition ,Marcel Dekkerinc ,NewYork. 2. Chow ,S.T. and Mcauliffe ,C.A. (1976) synthesis and biological studies of some amino acids complexes with Cu(ΙΙ) ,Mu(ΙΙ), Inorg. Nucl. chem. Lett, 8 (913):311-313. 3. Mcauliffe ,C.A. and Lavason, w. (1976) synthises and biological effect of some amino acid derivatives, Inorg. chem. Trans. Elem. 4(218):512-515. 4. Manuel ,A.V. ; Riberlo D.; Luis M.N.Sautos , B.F ; Faiia C.P. and Filipas, A.S. (2010) Energetic of Lead (ΙΙ) , Cadimium (ΙΙ) and Zinc (ΙΙ) chomplexes with amino acids , J.of Therm. Anal. And calorimetry 100( 2):310-312. 5. Hosney ,N.M. and El.Dossoki F.I (2008) Schiff Base complexes derived from 2-Acetyl- pyridive , leucine and some metal chlorides their preparation .characterization and physical properitis ; J. chem. Eng. Data ,53 :11. 6. Brij ,B.T. (2010) paper Electrophoritic Technique in the study of Berylinm(ΙΙ) ,cobalt (ΙΙ) proline binary complexes in solution , Bev. Soc. Quinsperui 76 (3):212-215 . 7. Al-Mudhufar D.M.; Al-Edani D.S. and Dawood s. (2010) synthesis charact-erize and biological activity of some complexes of some new amino acid derivatives , Journal of Korean chemical society 54(5):66-68. 8. Kabbani , A.T. ; Ramadan ,H. ; Hamad H.H. ; Ghannoum , A. and moineline ,Y. (2005) synthesis of some metal complexes of [N.(benzol) aminothioxomethyl] amino-acids ,J. aniv. Chem. Tech. and Met. 40 (33):40-44 . 9. Silverstien ,R.M;Webster , I.x. and Kiemle ,D.G.(2005) spectrometric Identification of organic compounds 7th edn. , John willy and sons Inc,Nj,USA. 10. Shankaranar ,M.L. and pated ,C.C. (1965) Infrared absorption studies on some derivations of xanthic dithiocarbanic, trithiocarbanic acid ,Spectro .chem. Acta ,21(5):95- 103 . 11. Naamato ,K. and Kieft ,X. (1967) Infrared spectra of some platinum(ΙΙ) glycine complexes , J.Inorg. Nucl. chem 29:2561-2568 . 12. Maractoriglano ,G.; Menabne ,L. and pellaani ; G.C. (1975) Exchange interaction synthises of spectroscopic and magnetic properties of mixed-ligand complexes of copper(ΙΙ) with Imidazol and nitrogen. Protect at amino acids ,J.Inorg. Nucl. Chem. 47(11):2212-2218 . 13. Kothari, V.M. and Busch , D.H. (1996) .photo chemistry of Cobalt (ΙΙΙ) complexes containing asulphinate .s ligand ,Inorg. Chem. , 8:2276-2280 . 14. Patil ,S.S., Thakar ,G.A. and shauka, M.M. (2011) ,Synthises characterization and antibacterial studies on some mixed ligand thorium complexes with N. and o. doner ligands, Acta. Polo. Pharm. Drug 68(6):881-887. 15. Al-Mudhaffar, D.M.; Al-Edani ,D.S. and Dawood ,S.M.(2010) synthesis , characterization and biological activity of some complexes of some new amino acid derivatives N-[(Benzolamino)-thioxomethyl] Amino acid ,J. chem. Soc. ,54(5):506-514 . 16. Nichllis ,D. (1979) complexes and first-row transition elements 1st edn. , Macmilolan chemistry text , London . 17. Lever A.B (1968) Inorganic spectroscopy ,1st Edition ,Elserier publishing company, NewYork . 18. Al-Hashimi , S.M. ; Sarhan ,B.M. and Jarad ,A.J. (2004) synthesis and identification of N-actyglycine with some metal salts ,Ibn -Al-Hatham J. for pure appl. Sci. 17(2):50-54 . 19. Triginno , M.G. ; Menabul , p. and saladini ,M. (1979) Inorgnic chemical acta 32(2):149-155 . 20. Battaglia , L.P. ; Bonamartin ,C.A.; marcotrigiano, G.L. and pellacani ,G.C. (1980) alpha and beta carboxylic group as primary ligating group in promoting amid deproto – 229 | Chemistry ` @1a@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹26@@ÖÜ»€a@I1@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (1) 2013 nation solid state behavior of N-tosylaninale copper(ΙΙ) complexes ,J. Am. Chem.Soc.(102):8-19 . 21. Huheey ,J.E. (1983) Inorganic chemistry principle of structure and reactivity,3rd Edition ,Harpar International S1 Edition ,Maryland . Table (1) : Physical properties for free ligand and its complexes Complexes M.wt Color m.p or D. M% Calculate (Found) Molar conductivity (ohm-1m2.mol -1 In(DMF) 10-3 M μ eff (B.M) Ligand(ATV) 218 Yellow 1350 C 17 [Co(ATV)2] 492.93 Deep-blue 250 0 d 11.96 (12.1) 23 4.60 [Ni(ATV)2] 492.71 Green 230 0 d 11.92 (10.9) 27 3.26 [Cu(ATV)2] 497.5 Deep-green 188 0 d 12.77 (12.1) 22 1.74 [Zn(ATV)2] 499.4 Yellow 225 0 d 13.1 (12.08) 25 0.00 [Cd(ATV)2] 546.4 Yellow 210 0 d 20.57 (20.1) 32 0.00 [Hg(ATV)2] 635 Yellow 2250 d 31.59 (32,2) 23 0.00 d= decomposition Table (2) : The characteristic infrared of ligand (ATV) and its complexes υ (M-O) υ (M-N) υ(OCO)sym υ(COO)asym υ(N-H) complexes ___ ___ 1315 (m) 1728 (s) 3369 (s) ligand (ATV) 570 402 1388 (m) 1629 (b) 3396 (b) (Co (ATV) 2) 450 401 1400 (s) 1635 (m) 3383 (m) (Ni (ATV) 2) 499 418 1438 (s) 1583 (S) 3421 (m) (Cu (ATV) 2) 425 418 1435 (s) 1622 3462 (b) (Zn (ATV) 2) 472 426 1417 (m) 1597 (S) 3421 (m) (Cd (ATV) 2) 472 426 1417 1506 (S) 3442 (b) (Hg (ATV) 2) Table (3):UV–visible absorption for the ligand (ATV) and its complexes in DMF( 10-3 M) Assignment Єmax. L. mol-1 cm-1 υ cm-1 λ (nm) complexes Π →Π* n → Π* 848 35 3 36496 30487 274 329 Ligand(ATV) C.T. 4A2 → 4Tg(p) 3991 151 35211 18656 284 536 {Co (ATV) 2} C.T. 3T1(F)→ 3T1 (p) 2329 65 42016 26881 238 272 {Ni (ATV) 2} C.T 2T2→ 2E 827 11 36363 12062 270 829 {Cu (ATV) 2} C.T. C.T 2235 292 38461 30395 260 329 {Zn (ATV) 2 C.T C.T 1707 1586 35842 30581 279 327 Cd (ATV) 2 C.T C.T 713 249 30487 27322 328 366 Hg (ATV) 2 C.T = charge transfer 230 | Chemistry `@1a@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹26@@ÖÜ»€a@I1@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (1) 2013 Fig. (1) : H1NMR spectrum of the ligand ATV. Fig. (2) : FT-IR spectrum of the ligand ATV Fig. (3) : FI- IR spectrum of the complex [Hg (ATV)2] 231 | Chemistry `@1a@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹26@@ÖÜ»€a@I1@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (1) 2013 Fig. (4) : UV – Visible spectrum of the ligand ATV Fig. (5) : UV – Visible spectrum of the complex Cu ( ATV)2 232 | Chemistry `@1a@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹26@@ÖÜ»€a@I1@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (1) 2013 تحضیر وتشخیص بعض المعقدات الفلزیة للیكاند N]- (استیل آمینو) فالین ]ثایوكسو مثیل عالیة سلمان قندیل جــامعـة بغــداد / )ابـن الھیثــم (كـلـیة التربــیة للعلوم الصرفة /قســم الكیــمیــاء 2012األول تشرین 22قبل البحث في: 2012آیار 6استلم البحث في : الخالصة سیانات مع الحامض -(مثیل امینو)ثایوكسو مثیل) فالین بوساطة تفاعل استیــــــــــل ایزوثایوN-حضر اللیكاند الجدید ( ) ، وقد شخص اللیكاند مــع معقداتھ المحضرة بالطرائق الطیفیة المتوفرة وھي (طیف الرنین النووي ATVاالمیني فالین ( ) ، االشعة فوق البنفسجیة والمرئیة واالشعة تحت الحمراء ، وقیاس نسبة الفلـــــز بوساطة H1NMRـــــــــي (المغناطیســ فضال عن قیاس التوصیلیة الموالریــــــــة ، الحساسیة المغناطیسیة . من نتائج ھذه A.A.Sطیف االمتصاص الذري اللھبي لھا الشكل الھندسي رباعي السطوح ) ، التي اقترح ATV( M(2الدراسات اعطت الصیغة المقترحة العامة لھذه المعقدات : ( Hg+2 ,Cd+2 , Zn+2 ,Cu+2 , Ni+2 ,Co+2 = Mإذ =ATV ي (اللیكاند االیون-N (استیل امینو) ثایوكسو مثیل) فالـــــین : فالین ، استیل ایزوثایو سینات ، المعقدات الكلمات المفتاحیة 233 | Chemistry Alia S. Kindeel Abstract Keywords : valine, acetylisothiocynate complexes Introduction Experimental Instruments Synthesis of the ligand Synthesis of the complexes Results and discussion Spectral studies HP1PNMR spectrum for the ligand (ATV) Infrared spectra The FT-IR spectra of complexes Electronic spectral The spectra of complexes References Table (1) : Physical properties for free ligand and its complexes Table (2) : The characteristic infrared of ligand (ATV) and its complexes Table (3):UV–visible absorption for the ligand (ATV) and its complexes in DMF( 10P-3P M) C.T = charge transfer Fig. (1) : HP1PNMR spectrum of the ligand ATV. Fig. (2) : FT-IR spectrum of the ligand ATV عالية سلمان قنديل قســم الكيــميــاء / كـلـية التربــية للعلوم الصرفة) ابـن الهيثــم) / جــامعـة بغــداد استلم البحث في : 6 آيار 2012 قبل البحث في:22 تشرين الأول 2012 الخلاصة