@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹1a26@@ÖÜ»€a@I2@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (2) 2013 Synthesis And Characterization Of Some New Metal Complexes Of Ethyl Cyano (2-Methyl Carboxylate Phenyl Azo Acetate) B. M. Sarhan R. M. Rumez H. A. Hassan Dept. of Chemistry/College of Education For Pure Science(Ibn Al-Haitham)/ University of Baghdad Received in : 17 April 2012 ، Accepted in : 20 November 2012 Abstract Complexes of (Co2+, Ni2+, Cu2+, Zn2+, Cd2+ and Hg2+) with the ligand Ethyl cyano (2- methyl carboxylate phenyl azo acetate) (ECA) have been prepared and characterized by FTIR, (UV-Visible), Atomic absorption spectroscopy, Molar conductivity measurements and magnetic moments measurements. The following general formula has been suggested for the prepared complexes [M(ECA)2]Cl2 where M = (Co2+, Ni2+, Cu2+ ,Zn2+, Cd2+, Hg2+) and the geometry is octahedral. Key words: Ethyl cyano (2-methyl carboxylate) phenyl azo acetate, complexes. 178 | Chemistry @@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹1a26@@ÖÜ»€a@I2@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (2) 2013 Introduction Azo compounds are very important class of chemical compounds receiving attention in scientific research, they are highly colored and have been used as dyes and pigments for along times[1,2]. Transition metal azo complexes have played an important role in the development of coordination chemistry and have wide application in industry and biological systems[3-8]. Rafid[9] prepared the azo dye 2-(2-pyridal azo)1,8-dihydroxy naphthalene and their complexes with some transition metals. A series of Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) complexes of azo-compounds containing hydroxyl quinoline moiety have been synthesized and characterized by elemental analysis, molar conductance, magnetic moments, IR, electronic and ESR spectral studies. The thermal analysis of the complexes was also used to confirm the structures of the complexes[10]. In this paper, we described the preparation and characterization of some new metal ions complexes with Ethyl cyano (2-methyl carboxylate phenyl azo acetate) (ECA). Experimental All chemical used were of reagent grade (supplied by either Merck or Fluka) and used as supplied. 1HNMR spectrum was recorded using Ultra Shield 300 MHz, Bruker, Switzerland, at University of Al al-Bayt, Jordan. The FTIR spectra in the (4000-400) range cm-1 were recorded as KBr disc on Shimadzu FT infrared spectrophotometer. (UV-Vis) spectra were recorded using (Shimadzu UV-Vis. 160A) (UV-Vis) spectrophotometer in ethanol solution (10-3 M), Metal contents of the complexes were determined by atomic absorption technique using Shimadzu AA680G Atomic absorption spectrophotometer. Magnetic moments (μeff B.M) were measured employing Faraday method using balance magnetic susceptibility model, MSBMKT, melting points were determined by using Stuart-melting point apparatus. Conductivity measurements were carried out using Philips PW. Digital conductivity meter. Synthesis of the ligand ethyl cyano (2-methyl carboxylate phenyl azo acetate) (ECA) A solution of methyl-2-amino benzoate (1.3ml, 0.01mole) in concentrated HCl (3ml) was cooled to (0-5˚C), a cooled solution of sodium nitrite (1.5g in 10ml of water) was added dropwise during 10 minutes, then the reaction mixture was stirred for 30 minutes at the same temperature. The mixture was added to an ice-cold mixture of ethyl cyano acetate (0.01mole) and sodium acetate (4.1g, 0.05mole) in ethanol (30ml) dropwise with stirring over 15 minutes. Afterwards the stirring was continued for 30 minutes and the reaction mixture then left to stand at room temperature for 2 hours. The solid product formed was collected and recrystallized from ethanol to give the orange crystals (ECA), m.p (142-144˚C), yield (75%) scheme (1). 179 | Chemistry @@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹1a26@@ÖÜ»€a@I2@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (2) 2013 NH2 COOCH3 NaNO2 HCl COOCH3 N+ NCl (A) COOCH3 N N CH COOC2H5 N C COOC2H5CH2 NC Scheme (1): Synthesis route for ligand (ECA) Synthesis of complexes A solution of metal chloride contains (0.11g, 0.11g, 0.076g, 0.061g, 0.091g and 0.122g) (1mmole) of CoCl2.6H2O, NiCl2.6H2O, CuCl2.2H2O, ZnCl2, CdCl2.H2O and HgCl2) respectively in ethanol was added to a solution of the ligand (ECA) (0.25g, 2mmole) in ethanol (5ml). After stirring for 3 hours colored precipitate was formed at room temperature, the rustling solids was filtered off, recrystalized from ethanol and dried at 50˚C. Results and discussion The isolated complexes were crystalline solids soluble in common solvents like ethanol, dimethyl formamide (DMF) and dimethyl sulphoxide (DMSO), the conductivity measurements in ethanol indicated electrolytic behavior. The molar ratio method was followed to know the ratio of metal ion to ligand in complexes. Ethanol was used as a solvent, the (M:L) ratio was found to be (1:2). Table (1) includes the physical properties; the magnetic measurements (μeff B.M) for the complexes. Spectra studies The 1HNMR spectrum of the ligand (ECA) was recorded in DMSO, Fig (1), showed the following signals: singlet (s) at δ(2.50) ppm for (DMSO), triplet (t) at δ(1.35) ppm for (3H, CH3), singlet (s) at δ(3.9) ppm for (3H, OCH3), quartet (q) at δ(4.34) ppm for (2H, OCH2) and multiplet (m) at δ(7.2-8.0) ppm for (4H, Ar-H). Infrared spectra The infrared spectra of ligand (ECA) and its complexes are given in Table (2). The strong absorption bands at the (1701) cm-1 and (2222) cm-1 in the free ligand, Fig (2) are due to υ(C=O) ester and υ(C≡N) [11,12], in the complexes spectral, Fig (3) for cobalt complex, the bands have been found in the range between (1637-1508) cm-1 shifted to lower frequencies by (64-193) cm-1 which indicates the coordination of the oxygen atom at the υ(C=O) group in methyl ester [13] and band of υ(C≡N) was absent which indicates the coordination through the nitrogen atom of υ(C≡N). The ligand spectrum showed a band at (1454) cm-1 due to υ(N=N)[14], the spectra of complexes show this band about (1436- 1373) cm-1 shifted to lower frequencies by (81-18) cm-1 which indicates the coordination 180 | Chemistry @@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹1a26@@ÖÜ»€a@I2@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (2) 2013 of the ligand (ECA) through the nitrogen atom of the azo nitrogen[15,16] and new bands appeared in the spectra of metal complexes at (530-510) cm-1 and (462-415) cm-1 attributed to the (M-O) and (M-N) respectively[17]. Electronic spectra The absorptions and assignments related to the ligand and its complexes are listed in Table (3), the ligand (ECA), Fig (4) exhibited an absorption bands at (253) nm (39525) cm-1 and (361) nm (27710) cm-1 which may be attributed to (π π*) and (n π*) transitions[18]. The spectra of complexes - [Co(ECA)2]Cl2 complex The spectrum of deep green complex of Co(II) exhibited the following bands at (40000) cm-1, (27472) cm-1, (15037) cm-1 and (12285) cm-1 which have been assigned to (C.T), 4T1g(F) 4T1g(P), 4T1g 4A2g and 4T1g 4T2g respectively[19]. The (B́ ) found to be (376.93) cm-1 and β = B́ / Bº comes out to be (0.388) which indicates the presence of covalent bond in the complex. The magnetic moment value for cobalt(II) complex is (4.34) B.M in the range of octahedral. - [Ni(ECA)2]Cl2 complex The spectrum of red complex, Fig (5) exhibited the following absorptions at (39840) cm-1, (27777) cm-1, (19920) cm-1 and (13071) cm-1 which have been assigned to (C.T), 3A2g 3T1g(P), 3A2g 3T1g(F) and 3A2g 3T2g respectively[20]. The (B́) was found to be (565.6) cm-1 and β = B́ / Bº comes out to be (0.543) which indicates the presence of covalent bond in the complex. The magnetic moment is (3.29) B.M confirmed the fore mention geometry. - [Cu(ECA)2]Cl2 complex The spectrum of deep red showed absorptions bands at (39370) cm-1 and (27548) cm-1 which were assigned to charge transfer transitions (C.T) and only one absorption band was observed at (19231) cm-1 which was assigned to 2Eg 2T2g transition[21,22]. The magnetic moment value for copper(II) complex is (1.75) B.M in the range of octahedral. - [Zn(ECA)2]Cl2, [Cd(ECA)2]Cl2 and [Hg(ECA)2]Cl2 The orange complexes of Zn(II), Cd(II) and Hg(II) showed only charge transfer of M L in the range (40000-27322) cm-1 because the electronic configuration of Zn(II), Cd(II) and Hg(II) which confirm the absence of any (d-d) transition[23]. According to spectral data as well as those obtained from elemental analysis, the chemical structure of the complexes suggested the octahedral, Fig (6). References 1. Zollinger, H. (1991) Color chemistry: synthesis, properties and application of organic dyes pigments, 2nd Ed., VCH publishers, New York. 2. Jinghai, X.; Jinqiu, X. and Defeng, Z. (2003) Research on some brown iron complex azo dyes, Chinese J. Chem. Eng., 11 (1): 65-72. 3. El- Baradie, K. Y.; Issa, R. M. and Gaber, M. (2004) Polymeric and binuclear monomeric Mn(II) chelates of some multidenate azo compounds derived from β- diketones, Indian J. Chem., 43A: 1126-1130. 4. Gaber, M.; Ayad M. M. and El-Sayed, V. S. (2005) Syntheses spectral and thermal studies of Co(II), Ni(II) and Cu(II) complexes of 1-(4,6-dimethyl pyrimidin-2-yl azo)- naphthalene-2-ol, Spectro Chim. Acta A, 62: 694-702. 5. Gup, R.; Giziroglu, E. and Kirkan, B. (2007) Synthesis and spectroscopic properties of 181 | Chemistry @@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹1a26@@ÖÜ»€a@I2@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (2) 2013 new azodyes and azo-metal complexes derived from barbituric and amino quinoline, Dyes Pigments, 73: 40-46. 6. Rageh, N. M. (2004) Toutomeric structures, electronic spectra, acid-base properties of some 7-aryl-2,5-diamino-3(4-hydroxy phenyl azo) pyrazolo-[1,5-a]pyrimidin-6- caronitrile) and effect of their Cu(II) complex solutions on some bacteria and fungi, SpectroChim. Acta A, 60: 1917-1924. 7. Tuncel, M.; Kahyaoglu H. and Cakir, M. (2008) Synthesis, characterization and biological activity of novel polydentate azo ligands and their Co(II), Cu(II) and Ni(II) complexes, Transit. Met. Chem., 33: 605-613. 8. Jarad, A. J.; Suhail, K. F. and Hussein, A. L. (2010) Synthesis and spectroscopic studies of new heterocyclic azo dye and their complexes with selected metal ion, AL-Mustansiriya J. Sci., 21 (6): 251-257. 9. Alsady, R. H. (2010) Preparation and spectrophotometric studies for azo dye 2-(2-pyridal azo)1,8-dihydroxy naphthalene and their complexes with some transition metals, J. Basrah Research, 36 (5): 98-109. 10. Gaber, M.; El-Hefnaw, G.; El-Borai, M. A. and Mohamed, N. F. (2011) Synthesis, spectral and thermal studies of Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) complex dyes based on hydroxyl quinoline moiety, J. Therm. Anal Calorim, 10: 1-9. 11. Lappert, M. F. (1962) Coordination compounds having carboxylic esters as ligands. Part II. Relative acceptor strengths of some Group III and IV halides, J. Chem. Soc., 542. 12. Dalton, F.; Hill, R. D. and Meakins G. D. (1960) The infrared spectra of deuterium compounds. Part I. The C–H stretching bands of OMe and NMe groups, J. Chem. Soc., 2927-2929. 13. Nakamoto, K. (1996) Infrared Spectra of Inorganic and Coordination compound, 4th Ed., John Wiley and Sons, New York. 14. Silverstein, R. M.; Bassler, G. C. and Morrill,T. C. (1981) Spectrometric Identification of Organic Compound, 4th Ed., John Wiley and Sons, Inc., New York. 15. Carballo, R.; Castiñeiras, A.; Covelo, B.; Niclós, J. and Vázquez-López, E. M. (2001) Synthesis and characterization of a potassium complex of magneson: [K(HL)(OH 2)2 ]... [H2L = 4-(4-nitrophenylazo)resorcinol (magneson)] ”, Polyhedron , 20 (18): 2415- 2420. 16. Pal, S.; Misra, T. K. and Sinha, C. (2000) Reaction of Ru(PPh3)3Cl2 with arylazoimidazoles: spectral characterisation and redox studies of [bis-{N(1)-alkyl-2- (arylazo)imidazole}-bis-(triphenylphosphine)]-ruthenium(II) perchlorate, Transition Met. Chem. 25 (3): 333-337. 17. ChandraseKharan, M.; Udupa, M. R. and Aravamudan, G. (1973) Cysteine complexes of palladium(II) and platinum(II) ”, Inorg. Chim. Acta, 7: 88. 18. Dyer, R. J. (1965) Application of Absorption Spectroscopy of Organic Compounds Prentice-Hall, Inc., Englwood Cliffs, N. J., London. 19. Speca, A. N.; Mikulski, C. M.; Iaconianni, F. J.; Pytlewski, L. L. and Karayannis, N. M. (1980) Purine complexes with divalent 3d metal perchlorates , Inorg. Chem., 19 (11): 3491-3495. 20. Jorgensen, C. K. (1963) Synthesis, characterization and antibacterial activity of Mn(II), Co(II), Ni(II) and Cu(II) complexes of 4-carboxaldehyde phenyl hydrazone 1-phenyl-3- methyl-2-pyrazoline-5-one, Advan. Chem. Phys., 5 (33): 22. 21. Menabue, G. M. and Peracani, G. C. (1979) Synthesis and spectroscopic, magnetic and structural properties of bis (N-acetyl-β-alanine) diaquacopper(II) and tetrakis (N-acetyl- β-alanine) diaquadicopper(II) dihydrate, Inorg. Chem., 39: 1897. 22. Massy, A. C. and Johnson, B. F. G. (1975) The Chemistry of Copper, Silver and Gold, Pergamon Press, Oxford, 20 and 41. 23. Maracotrigiano, G.; Menabue, L. and Pellancani, G. C. (1975) Complex formation of 182 | Chemistry @@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹1a26@@ÖÜ»€a@I2@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (2) 2013 Zinc(II) with glycine, N-acetyl and N-benzoyl-1-glycine anions in aqueous and ethanolic solution by polarographic method, J. Inorg. Nucl. Chem., 37: 2344. Table (1): Physical properties of ligand and its metal complexes Formula Molecular weight Colour M.p˚C or dec. Metal % Found (Calc.) Molar conductivity (S.cm2mole-1) in Ethanol (10-3 M) μeff (B.M) C13H13O4N3 [ECA] 275 Orange 142- 144˚C - 2.4 - [Co(ECA)2]Cl2 679.93 Deep green 95(dec.) 8.50 (8.66) 80 4.34 [Ni(ECA)2]Cl2 679.69 Red 100(dec.) 7.46 (8.64) 75 3.29 [Cu(ECA)2]Cl2 684.54 Deep red 98(dec.) 10.07 (9.28) 81 1.75 [Zn(ECA)2]Cl2 686.39 Orange 120(dec.) 9.56 (9.53) 82 0.00 [Cd(ECA)2]Cl2 733.4 Orange 130(dec.) 14.72 (15.33) 76 0.00 [Hg(ECA)2]Cl2 821.6 Orange 118(dec.) 23.84 (24.42) 72 0.00 Table (2): Characteristic infrared bands of the ligand (ECA) and its metal complexes Compound υ(N=N) υ(C=O) Ester υ(C≡N) M-N M-O C13H13O4N3 [ECA] 1454 1701(s) 2222(s) - - [Co(ECA)2]Cl2 1435(m) 1627(s) - 420(w) 526(w) [Ni(ECA)2]Cl2 1436(m) 1637(s) - 424(w) 530(w) [Cu(ECA)2]Cl2 1404(w) 1620(s) - 418(m) 520(w) [Zn(ECA)2]Cl2 1435(m) 1508(s) - 418(m) 518(w) [Cd(ECA)2]Cl2 1373(m) 1624(m) - 415(m) 516(m) [Hg(ECA)2]Cl2 1435(m) 1612(s) - 462(m) 510(w) Where: s = strong, m = medium, w = weak 183 | Chemistry @@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹1a26@@ÖÜ»€a@I2@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (2) 2013 Table (3): Electronic spectra data of ligand (ECA) and its complexes in ethanol solvent Compound λmax nm Wave number cm-1 εmax Molar-1cm-1 Assignment Ligand [ECA] 253 361 39525 27710 567 1207 π π* n π* [Co(ECA)2]Cl2 250 364 665 814 40000 27472 15037 12285 428 870 10 8 C.T 4T1g(F) 4T1g(P) 4T1g 4A2g 4T1g 4T2g [Ni(ECA)2]Cl2 251 360 502 765 39840 27777 19920 13071 365 869 12 8 C.T 3A2g 3T1g(P) 3A2g 3T1g(F) 3A2g 3T2g [Cu(ECA)2]Cl2 254 363 520 39370 27548 19231 1178 1497 143 C.T C.T 2Eg 2T2g [Zn(ECA)2]Cl2 253 366 39525 27322 422 915 ILCT ILCT [Cd(ECA)2]Cl2 254 361 39370 27472 421 989 ILCT ILCT [Hg(ECA)2]Cl2 250 362 40000 27624 323 720 ILCT ILCT ILCT: Internal Ligand Charge Transfer Fig. (1): 1HNMR spectrum of ligand (ECA) 184 | Chemistry @@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹1a26@@ÖÜ»€a@I2@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (2) 2013 Fig. (2): Infrared spectrum of ligand (ECA) Fig. (3): Infrared spectrum of [Co(ECA)2]Cl2 Fig. (4): Electronic spectrum of ligand (ECA) 185 | Chemistry @@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹1a26@@ÖÜ»€a@I2@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (2) 2013 Fig. (5): Electronic spectrum of [Ni(ECA)2]Cl2 C N N CH OCH3O M Cl2 [M(ECA)2]Cl2 (M+2 = Co, Ni, Cu, Zn, Cd, Hg) C N NCH O OCH3 C O OC2H5 C N N C O C2H5O C Fig .(6): The proposed structural formula of the complexes 186 | Chemistry @@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@@ÚÓ‘Ój�n€a@Î@Úœäñ€a@‚Ï‹»‹€@·rÓ:a@Âig@Ú‹©@Ü‹1a26@@ÖÜ»€a@I2@‚b«@H2013 Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 26 (2) 2013 تحضیر وتشخیص بعض المعقدات الفلزیة الجدیدة مع اللیكاند اثیل سیانو مثیل كاربوكسلیت فنیل ازو خالت) -2( باسمة محسن سرحان رسمیة محمود رمیز ھدى احمد حسن د/ جامعة بغداالكیمیاء/ كلیة التربیة للعلوم الصرفة ( ابن الھیثم) علوم قسم 2012تشرین الثاني 20، قبل البحث في : 2012نیسان 17استلم البحث في : الخالصة مثیل كاربوكسلیت فنیل ازو خالت) مع ایونات -2حضرت بعض المعقدات الفلزیة الجدیدة مع اللیكاند اثیل سیانو( ) )Co(II ) ،Ni(II ) ،Cu(II ) ،Zn(II ) ،Cd(II )وHg(II وشخصت بالطرائق الطیفیة وھي طیف االشعة تحت ( الحمراء، وطیف االشعة فوق البنفسجیة والمرئیة فضال" عن تعیین نسبة الفلز في المعقدات بوساطة طیف االمتصاص لفلز، وقیاس الذري، وقیاس التوصیلیة الموالریة لمحالیل المعقدات في مذیب االیثانول، وتحدید النسبة المولیة للیكاند الى ا العزم المغناطیسي للمعقدات المحضرة. وفي ضوء التشخیصات اعاله اقترح الشكل الثماني السطوح لھذه المعقدات. مثیل كاربوكسلیت فنیل ازو خالت)، معقدات. -2: اثیل سیانو(الكلمات المفتاحیة 187 | Chemistry