Conseguences of soil crude oil pollution on some wood properties of olive trees Chemistry |211 https://doi.org/10.30526/30.3.1617 7302(عام 0العدد ) 03مجلة إبن الهيثم للعلوم الصرفة والتطبيقية المجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (3) 2017 Synthesis, Characterization and Biological Evaluation of New Dithiocarbamate Ligand and Its Complexes with some Metal Ions Ahmed T. Numan Dept. of Chemistry/ College of Education for Pure Science (Ibn Al-Haitham)/ University of Baghdad. Kaiss R. Ibraheem Mohammed K. Ibrahim Dept. of Chemistry/ College of Science/ University of Anbar Received in:24/May/2017,Accepted in:6/September/2017 Abstract New bidentate dithiocarbamate ligand (NaL) namely [Sodium-2-(((3-methyl -4- “(2,2,2-tri fluoro ethoxy) pyridin-2”-yl) methyl) sulfinyl)-1H-benzoimidazole -1-carbodithioate] was prepared. This free ligand was synthesized from the reaction of a (RS)-2-([3-methyl -4-(2,2,2-tri fluoroethoxy) pyridin-2-yl] methyl sulfinyl)-1H benzoimidazole, CS2 and NaOH in methanol as solvent. From reaction of dithiocarbamate salt (NaL) with metal ions (M); Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Pd(II)”, have obtained the DTC complexes at general molecular formula [M(L)2(H2O)2] and [Pd(L)2]. To characterize the ligand and its complexes, used different analyses methods such FTIR, UV-Vis, elemental microanalysis, atomic absoreption, magnetic susceptibility, conductance, melting points, 1 H- 13 C- NMR spectroscopy, thermal analysis and mass spectrum. These studies indicated the formation of DTC complexes which their geometries about metal centers are octahedral; except Pd-complex is square planer. The bacterial activity evaluation against investigated bacterial species indicated that the metal complexes are more active than the free ligand when compared them. Keywords: Dithiocarbamate complexes; metal ions; Characterization; Bacterial activity. Chemistry |212 https://doi.org/10.30526/30.3.1617 7302(عام 0العدد ) 03مجلة إبن الهيثم للعلوم الصرفة والتطبيقية المجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (3) 2017 Introduction “ Dithiocarbamates (DTC) are organic compounds, which played an important role in the development of chemistry, especially in coordination chemistry field”. This is due to strongly chelating ability towards metal ions [1,2]. The high ability of dithiocarbamates (DTC) to react with transition metals allowed them to be as useful ligands in both inorganic and bioinorganic chemistry. This is based on the sway of the anionic N-CS2¯ moiety that has a variety of binding modes; mono, bi and bridging-dentate capable to form very stable complexes [3,4]. Interestingly, DTCs can be stabilised at a different oxidation states of metals, the compounds form and coordination geometries that show great structural diversities which range from monomeric to polymeric molecular [5,6]. The most common structural arrangements were the square planar and octahedral geometries [7]. The great applications are contributed considerably in developing the dithiocarbamates and their complexes, where included; Biomedical applications [8], analytical chemistry applications [9], environmental applications [10], agriculture applications and in the industry [11]. Also it investigates about the influence of dithiocarbamates against bacteria, fungi and microorganisms [12]. In this paper we report about synthesis, characterisation and bacterial evaluation of new dithiocarbamate ligand and its metal complexes. Experimental “ All reagents used were analar or chemically pure grade by British drug”house (BDH), Sigma-Aldrich,Merck and Fluka”. Metal salts (CoCl2.6H2O, NiCl2.6H2O, CuCl2.2H2O, ZnCl2, CuCl2.2H2O and PdCl2), (RS)-2-([3-methyl -4-(2,2,2-tri fluoroethoxy) pyridin-2-yl] methyl sulfinyl)-1H benzoimidazole, Carbon disulfide, DMSO, Ethanol and Methanol. Instrumentations 1 H and 13 C-NMR were recorded using ultra shield 400 MHz Switzerland at Kharazmi University, Iran, conductivity measurements were carried out by Philips PW digital meters conductivity in DMSO at 10 -3 M, “FT-IR spectra were recorded as KBr discs in the range 4000-400 cm -1 using Shimadzu 8300s FT-IR spectrophotometer and as CsI discs in the range 400-200 cm -1” .”UV-Visible spectra were recorded by Shimadzu UV-8300 vis160A ultraviolet spectrophotometer the range of (200-1100) nm at 10 -3 M in DMSO”. Metal contents of the complexes were determined by flame atomic absorption using (Shimadzu at A.A 680 GBC 933 plus) atomic absorption spectrophotometer, magnetic susceptibility (μeff. B.M) were recorded by faraday method using balance magnetic susceptibility model (Sherwood Scientific). Melting point was determined by using (Stuart-melting point apparatus).“Determinations of (C, H, N and S) content for prepared compounds were carried out using Heraeus instrument (Vario EL)”. Thermogravimetric analysis (TGA) was carried out using an STA PT-1000 Linseis company and mass spectrum by Shimadzu GC-Mass QPA-2013 spectrometer. Synthesis of free ligand A standard method was used in the synthesis of dithiocarbamte compounds [13], it was used with a slight modifications to prepare the free ligand Sodium 2-(3-methyl-4-(2,2,2- trifluoroethoxy)pyridin-2-yl)methyl)sulfinyl)-1H-benzoimidazole-1-carbodithioate (NaL). Mixed equimolar amounts from reactors in following; (1 g, 2.70mmol) of (RS)-2-([3-methyl- 4-(2,2,2-trifluoroethoxy)pyridin-2-yl] methylsulfinyl)-1H benzoimidazole was dissolved in 20ml of absolute methanol in a round bottom flask, then was added (0.10g, 2.70mmol) of sodium hydroxide dissolved in 2ml of double distilled water. The mixture was allowed to stir in a room temperature about 30 minutes and then was placed in ice bath. To this cold solution Chemistry |213 https://doi.org/10.30526/30.3.1617 7302(عام 0العدد ) 03مجلة إبن الهيثم للعلوم الصرفة والتطبيقية المجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (3) 2017 a pure carbon disulfide (0.163ml, 0.20g, 2.70mmol) was added drop-wise with constant stirring. The mixture was maintained at 0 °C for 4 h to result pale yellow solution then it was allowed at room temperature to evaporate, all of that was cleared in scheme (1). Sodium salt of dithiocarbamate was formed as a pale yellow powder, dried and recrystallized by methanol, washed several times by diethylether, decomposed at 201-203ºC. Yield:“66.67% and elemental microanalysis C.H.N. and S. were listed in Table(1)”. Synthesis of [Ni(L)2(H2O)2] complex “ A general method was used to achieve dithiocarbamate complexes[14,15]”.“A solution of (0.101g, 0.425mmol) NiCl2.6H2O in 10ml ethanol was added drop wise to a round bottom flask, volume (100) ml, which contains a solution of (0.4g, 0.850mmol) of the dithiocarbamate ligand salt (NaL), dissolved in 10ml of ethanol. The reaction mixture was stirred and heated under reflux for 4 h, then was left to evaporate at room temperatures”. The resulted solid washed with distilled water then by diethyl ether, dried at room temperature to give a pale green solid, m.p= 271 ºC. Yield: 0.242g (57.81%), Scheme (2) showed that. Synthesis of [Co(L)2(H2O)2], [Cu(L)2(H2O)2], [Zn(L)2(H2O)2], [Cd(L)2(H2O)2], [Pd(L)2] complexes. “A similar method to that mentioned in preparation of [Ni(L)2(H2O)2] complex with same quantitatives, was used to prepare NaL complexes with CoCl2.6H2O (0.101g, 0.425mmol), CuCl2.2H2O(0.072g, 0.425mmol), ZnCl2 (0.058g,0.425mmol), CdCl2.2H2O (0.093g, 0.425mmol) and PdCl2 (0.075g, 0.425mmol).“Table (1) displays some physical properties of the prepared complexes, and elemental microanalysis C.H.N. and S. for some prepared complexes”. Results and Discussion “ The dithiocarbamate ligand (NaL) was synthesized in one step. The structure of (NaL) was checked and confirmed by elemental miocranalyses data (Table (1)), which is in good agreement with proposed formula C17H13F3N3NaO2S3”. IR Spectrum of the ligand (NaL) “ The FTIR spectrum of Sodium2-(((3-methyl-4-(2,2,2trifluoroethoxy) pyridin-2-yl) methyl)sulfinyl)-1H-benzo[d]imidazole-1-carbodithioate(NaL) Figure (1), is compared with the FTIR spectra of the starting materials and carbon disulfide”.“The spectrum of NaL shows no band (disappeared) around 3222 cm -1 was assigned to υ(NH) stretching vibration, compared with that observed in the starting material [16]”.“The IR spectrum reveals new band at 1446 cm -1 can be attributed to υ(C-N) stretching of (N-CS2) moiety [17]”.“Also the IR spectrum reveals two new bands at 1055 cm -1 and 942 cm -1 attributed to υasy (CS2) and υsy (CS2), respectively [18]”.”The bands at 3062 cm -1 and 2990, 2943 cm -1 attributed to the υ(C– H) aromatic and υ(C–H) aliphatic stretching vibration respectively”.“The bands observed at 1630 cm -1 and 1587cm -1 were assigned to υ (C=N) and υaromatic(C=C) mode of aromatic system respectively“[19].“While the band observed at 1271 cm -1 recorded to υ (C–N) stretching vibration”[20]. On the other hand the spectrum displayed bands at 1188 cm -1 , 972 cm -1 and 663 cm -1 attributed to the υ(C–O–C), υ(C–S) and υ(C–F) respectively [21]. “The assignments of characteristic bands are summarized in Tables (2).” Electronic Spectrum of the ligand (NaL) The U.V-Vis spectrum of ligand NaL in DMSO solution, Figure (2) showed two absorption peaks, the first peak at (285 nm =35087 cm -1 ; εmax= 2401molar -1 cm 1 ) was assigned to π→π* Chemistry |214 https://doi.org/10.30526/30.3.1617 7302(عام 0العدد ) 03مجلة إبن الهيثم للعلوم الصرفة والتطبيقية المجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (3) 2017 electronic transition.”The second peak at (321 nm =31152 cm -1 ; εmax= 1728 molar -1 cm -1 ) was attributed to n→π* electronic transition”[22,23]. “The U.V-Vis spectral data of the ligand (NaL) were given in Table (3).” 1 H, “ 13 C-NMR spectra for the ligand (NaL)” “ The 1 H-NMR spectrum for the ligand NaL in Figure (3) showed the following characteristic chemical shift (DMSO-d 6 as a solvent)”: The spectrum showed the singlet signal at =8.35 ppm is assigned to proton for C14. The singlet chemical shifts at =7.57 ppm and 7.55 ppm are assigned to protons for C7 and C4 respectively. The signal at chemical shift =7.54 ppm is assigned to the proton for C15. The multiple chemical shifts at =7.10 ppm and 7.09 ppm refers to the protons of the C6 and C5 respectively. A signal at δ= 4.54 ppm attributed to the two protons for C19 of methylene group, While a multiple signal at δ= 4.36 ppm attributed to the two protons for C11 of another methylene group. The chemical shift at δ=2.51 is assigned to DMSO solvent. The chemical shift at δ=2.19 is assigned to the three protons for C18 of methyl group. The NMR spectral data of ligand was reported in literatures [24,25]. The 13 C-NMR spectrum of a ligand NaL, Figure (4) in DMSO-d 6 solvent showed that the chemical shift at = 192.3 ppm attributed to carbon atom C10 for S=C-S of dithiocarbamate group [4]. The carbon atoms C16 and C12 resonated with the chemical shifts at δ= 161.2, 160.1 ppm respectively. The carbon atom C14 resonated with the chemical shift at δ =152.4 ppm. The carbon atoms C2, C9 and C8 resonated with the chemical shifts at δ = 148.0, 144.7 and 127.9 ppm respectively. The carbon atoms C5 and C6 resonated with the chemical shift at δ = 125.1 ppm. The carbon atom C20 of C-F3 group resonated with the chemical shift at δ =122.4 ppm. Also the carbon atoms C4 and C7 resonated with the chemical shifts at δ=121.9, 119.5 ppm respectively. While the carbon atoms C17, C15 resonated with the chemical shifts at δ= 117.0, 106.7 ppm respectively. The carbon atom C19 for C-O resonated with the chemical shift at δ= 73.8 ppm, While the carbon atom C11for C-S=O resonated with the chemical shift at δ= 60.1 ppm. The chemical shift at δ=40.06 ppm attributed to DMSO solvent. Finally the chemical shift at δ =10.5 ppm attributed to the carbon atom C18 of methyl group. The 13 C- NMR spectral data of ligand was reported in literatures [9,26]. Mass Spectrum of the ligand (NaL)” “ The electrospray (+) mass spectrum of NaL is exhibited successive fragments related to ligand s'tructure”.”The parent ion peak for the ligand is observed at m/z = 467.6 which corresponds to M + (15%) for C17H13N3NaO2S3F3; requires = 467.4. The other peak fragments are shown in Figure (5).” The IR Spectra for the DTC Complexes The FTIR spectrum of [Co(L)2(H2O)2], Figure (6),”exhibits bands related to the ligand with the appropriate shift due to complex formation”. “The spectrum displays band at 1629 cm - 1 , which is related to ν(C=N) moiety, when the band at 1587 cm -1 was assigned to νar(C=C) modes of aromatic system”.”Also the spectrum was displayed band at 1469 cm - 1 , which is related to ν(N-CS2) mode, compared with that detected in the free ligand at 1446 cm -1” .”The complex exhibited two bands, which are attributed to the asymmetric ν(CS2) at1055 cm -1 and symmetric ν(CS2) at 942 cm -1 stretching”.”These bands are characteristic for an anisobidentate chelating mode of the ligand to the metal ions[27,28]”.”At lower frequency (far FTIR) complex [Co(L)2(H2O)2], exhibited two bands at 393cm -1 and 375cm -1 that are assigned to the ν(M-S) vibrational mode and supporting the anisobidentate chelation mode of the ligand [27]”.”The νar(C-H) stretching of the aromatic ring which occurs slightly above 3000 cm -1 is observed at 3068 cm -1 , when the ν(C-H) stretching for the aliphatic group is Chemistry |215 https://doi.org/10.30526/30.3.1617 7302(عام 0العدد ) 03مجلة إبن الهيثم للعلوم الصرفة والتطبيقية المجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (3) 2017 detected at 2939 cm -1” [19]. Also the IR spectrum exhibited broad band at 3471cm -1 and new' band at 816cm -1 that may be attributed to υ(OH) and δ(OH) respectively which refer to coordinated H2O molecule (aqua) with Co-complex in molecular formula [29].”The FTIR spectra for [Ni(L)2(H2O)2], [Cu(L)2(H2O)2], [Zn(L)2(H2O)2], [Cd(L)2(H2O)2] and [Pd(L)2] complexes, Figures (7) show similar trend to that of the [Co(L)2(H2O)2] complex and same reasoning could be used to interpret the spectrum, all the results are summarized in table (2).” The Electronic Spectra and Magnetic Studies for the DTC Complexes The electronic spectrum of Co II -complex, exhibits five peaks, The first and second peaks at (279 nm=35842 cm -1 ) and (353 nm= 28328cm -1 ) were assigned to the ligand field (L.F), while the third peak at(401 nm=24937 cm -1 ) is due to charge transfer transition. The peaks at visible region (d-d) at (565 nm=17699 cm -1 ), (724 nm=13812 cm -1 ) due to the d-d electronic transition typ ( 4 T1g(F)→ 4 T1g(P)) and ( 4 T1g(F)→ 4 A2g(F)) respectively, transitions confirming an octahedral structure around Co(II) central metal ion [30].”The magnetic susceptibility measurement for the solid Co(II) complex is (4.86) B.M. also is indicative of three unpaired electron per Co(II) ion suggesting consistency with its octahedral environment[31].” The electronic spectrum of Ni-complex showed peaks in the (281nm=35587 cm -1 ) and (352 nm= 28409cm -1 ) were assigned to the ligand field. And another peak in the (390nm=25641 cm -1 ) due to charge transfer transition. And the peaks at visible region at (837 nm=11947 cm -1 ) and (937nm=10672 cm -1 ) due to the d-d electronic transition. These peaks are assigned to ( 3 A2g→ 3 T1g(P)) and ( 3 A2g→ 3 T2g(F)) respectively, transitions confirming an octahedral structure around Ni (II) ion complex [32].”The magnetic susceptibility measurement for the solid Ni(II) complex is (2,9) B.M. also is indicative of two unpaired electrons per Ni (II) ion suggesting consistency with its octahedral geometry[31].” The electronic spectrum of Cu-complex showed two peaks in the range (274 nm=36496 cm -1 ) and (352nm=28409 cm -1 ) are assigned to the ligand field. And another peak in the range (371 nm=26954 cm -1 ) is due to charge transfer transition. The peak at visible region at (722 nm=13850cm -1 ) is due to the d-d electronic transition type.”This peak is assigned to ( 2 Eg→ 2 T2g) transition confirming a distorted octahedral structure around Cu(II) ion complex [33].”The magnetic susceptibility measurement of Cu(II) complex is (1.89) B.M., which suggests the presence of one unpaired electron with its octahedral environment[31].” The electronic spectral of Zn II -and Cd II - complexes. In each case the spectrum showed three intense peaks in the U.V region at (274nm=36496cm -1 , 368nm=27173cm -1 ) and (277nm=36101cm -1 , 347nm=28818cm -1 ) for Zn II and Cd II - complexes respectively, assigned to the ligand field. While the peaks at (406nm=24630cm -1 ) and at (401nm=24937cm -1 ) are assigned to the charge transfer transitions. Finally the metal ion of these complexes belongs to d 10 system and these metals do not show d–d transition. These complexes are diamagnetic as expected and it showed octahedral geometries [34,35]. The electronic spectrum of Pd-complex, Figure (8) showed two peaks in the range (302 nm=33112 cm -1 ) and (345nm=28989cm -1 ) are assigned to the ligand field. And another peak in the range (380 nm=26315 cm -1 ) due to charge transfer transition. The peaks at visible region at (719 nm=13908cm -1 ) and (804 nm=12437cm -1 ) due to the d-d electronic transition type. These peaks are assigned to ( 1 A1g→ 1 B1g) and ( 1 A1g→ 1 E1g) respectively, transitions confirming a square planer structure around Pd(II) ion complex, This complex is diamagnetic [36]. Electronic spectral data and magnetic susceptibility for these complexes are summarised in table (3) Chemistry |216 https://doi.org/10.30526/30.3.1617 7302(عام 0العدد ) 03مجلة إبن الهيثم للعلوم الصرفة والتطبيقية المجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (3) 2017 Thermal analysis The thermal analysis curve (TGA) for [Cd(L)2(H2O)2] is shown in Figure (9). The thermogram revealed that the complex is stable up to 78 ° C in helium atmosphere.”It is decompose in four steps. The first step observed at 78.4-193 ° C attributed to the loss of (2H2O) fragment, (obs.= 0.5700 mg, 3.00%; calc.= 0.6594 mg, 3.471%).”The second step occurred at 193-319 ° C indicated to the loss of (C14H11N3OS2F3+CS2) fragment, (obs.= 8.1624 mg, 42.96%; calc.= 7.9515mg, 41.85%)”.”The third step occurred at 319-415 ° C indicated to the loss of (C12H8NOF3+CS2) fragment, (obs.= 5.6335 mg, 29.65%; calc.= 5.8387mg, 30.73%)”. The fourth step found at 415-578 ° C indicated to the loss of (C6H7N2O) fragment, (obs.= 2.4795 mg, calc.= 16.703 mg, 87.912%) while, the residue of the compound is related to the (CdO), (obs.= 2.5346 mg, 13.34%; calc.= 2.2967mg, 12.09%)[37,38]. Thermal decomposition data for this complex is summarized in table (4). Molar Conductivity “ The molar conductance values of the the complexes in DMSO lie in the range”(8.2-18) ohm - 1 .cm 2 .mol -1 which is quite lower than that expected for an electrolyte and reveal their nonelectrolyte nature [9] as in table (1).” Bacterial activity The synthesised dithiocarbamate ligand (NaL) and its metal complexes were tested by using disc method inhibition (against four types of pathogenic bacteria, Escherichia coli and Pseudomonas aeruginosa (G−) that gram negative, Staphylococcus aureus and Bacillus stubtilis (G+) that gram positive. Data of the measured inhibition zones against growth of different bacteria’s are summarised in Table (5), which displays the effect of the synthesised compounds on bacterial strains. From obtained data, it is obvious that, the complexes are already more active against these bacterial specie compared with the free ligand, which means complexation increases antimicrobial activity. 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Housecroft, C. E. and Sharpe, A. G., (2008). “Inorganic Chemistry”, 3 rd Ed., Pearson Education Limited: Essex, England, 573-681. 32. Nami, S. A.; Husain, A. and Ullah, I., (2014). “Self- assembled homodinuclear dithiocarbamates: One pot synthesis and spectral characterization”, J. Spectrochimica Acta Part A: Mol. Bio Spectroscopy.,118. 380-388. 33. Lever, A. B. P., (1984). “Inorganic Electronic Spectroscop”, 2 nd. Ed., Elsevier publisher, NewYork. 34. Alyass, J. M. and Mohammed, A. F., (2012). “Synthesis and characterization of Co(II) , Ni(II), Cu(II) Zn(II) and Cd(II) mixed complexes of imidazol dithiocarbamate and 1,10- phenanthroline”., Iraqi Nat. J. Chem., 45.105- 116. 35. Shriver, D.W. and Atkins, P.W., (2006). “Inorganic chemistry, electronic spectra of TM complexes”. 4 th ed. Freeman, New York. 36. Karcz, D.; Matwijczuk, A.; Boron, B.; Creaven, B.; Fiedor, L.; Niewiadomy, A. and Gago, M., (2017).“Isolation and spectroscopic characterization of Zn(II), Cu(II), and Pd(II) complexes of 1,3,4 thiadiazole-derived ligand”, J. Molec. Struc., 1128. 44-50. Chemistry |219 https://doi.org/10.30526/30.3.1617 7302(عام 0العدد ) 03مجلة إبن الهيثم للعلوم الصرفة والتطبيقية المجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (3) 2017 37. Al-Hamdani, A. A. S.and Hamodha, R. G., (2016). “Transition metal complexes with tridentate ligand: preparation, spectroscopic characterization, thermal analysis and structure studies”, J. Bag. Sci., 13(4). 770-781. 38. Al Zoubi, W.; Al-Hamdani, A. A. S. and GunKo, Y.,(2017). “Schiff bases and their complexes: Recent progress in thermal analysis”, J. Separation Sci.Tech., 52(6). 1052- 1069. Table (1): Colours, yields, melting points, (C, H, N, S) analysis and molar conductance values for ligand and its dithiocarbamate complexes” Comp. M.wt g\mol m.p ºC Yield % Colour ᴧm S.Cm 2 molar - Microanalysis Found (calc) % M% C H N S NaL 467.47 201- 203* 66.67 Pale yellow - - 43.09 (43.68) 2.43 (2.80) 9.74 (8.99) 20.01 (20.57) [Co(L)2(H2O)2] 983.93 282* 55.25 Green 18.0 5.87 (5.99) (41.50) (3.07) (8.54) (19.55) [Ni(L)2(H2O)2] 983.69 271 57.81 Pale green 15.7 5.57 (5.97) 40.83 (41.51) 2.91 (3.07) 8.79 (8.54) 19.34 (19.55) [Cu(L)2(H2O)2] 988.55 279 61.36 Brown 10.9 6.58 (6.43) (41.31 (3.06) (8.50) (19.46) [Zn(L)2(H2O)2] 990.38 290* 48.74 White 8.9 6.01 (6.60) 41.06 (41.23) 2.98 (3.05) 8.41 (8.49) 18.85 (19.42) [Cd(L)2(H2O)2] 1037.4 326* 63.09 Yellow white 8.2 10.81 (10.84) (39.36) (2.91) (8.10) (18.54 [Pd(L)2] 995.39 296* 59.06 Brown 16.3 10.43 (10.69) 40.77 (41.03) 2.51 (2.63) 8.73 (8.44) 18.41 (19.33) *= decompose “Table (2): FT-IR data (wave-number) cm -1 of ligand and its metal complexes.” ν(M-O) ν(H2O) νas(CS2) ν,s(CS2) ν(C-O- C) ν(C- N) ν(N- CS2) νar (C=C) ν(C=N) νalip h(C- H) νarom (C-H) ν(OH) water Comp. _ _ _ 1173 1275 _ 1583 1631 2983 2927 3066 _ Starting materials _ _ 1055 942 1188 1271 1446 1587 1630 2990 2943 3062 _ NaL 607 816 1101 914 1173 1261 1469 1587 1629 2939 3068 3471 [Co(L)2(H2O)2]* 611 820 1109 922 1173 1261 1473 1591 1627 2966 3032 3439 [Ni(L)2(H2O)2] 621 814 1086 916 1170 1259 1470 1579 1631 2976 3078 3437 [Cu(L)2(H2O)2] 619 827 1113 915 1173 1275 1456 1579 1622 2972 3086 3444 [Zn(L)2(H2O)2] 580 825 1082 928 1176 1263 1464 1591 1647 2951 3070 3440 [Cd(L)2(H2O)2] _ _ 1047 918 1169 1257 1477 1581 1633 2966 2931 3080 _ [Pd(L)2] Chemistry |220 https://doi.org/10.30526/30.3.1617 7302(عام 0العدد ) 03مجلة إبن الهيثم للعلوم الصرفة والتطبيقية المجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (3) 2017 * (M–S) observed at 393cm -1 and 375 cm -1 “Table (3): UV-Vis spectral data of ligand and dithiocarbamate complexes in DMSO solutions and magnetic moment” Compound Wavenumber max molar –1 cm –1 Assignment Suggested structure μeff (B.M) nm Cm –1 NaL 285 35087 2401 → * _ _ 321 31152 1728 n→ * [Co(L)2(H2O)2] 279 353 35842 28328 2395 569 L.F L.F Oh 4.86 401 24937 365 C.T 565 724 17699 13812 34 32 4 T1g(F)→ 4 T1g(P) 4 T1g(F)→ 4 A2g(F) [Ni(L)2(H2O)2] 281 352 35587 28409 2435 637 L.F L.F Oh 2.90 390 25641 232 C.T 837 937 11947 10672 10 12 3 A2g→ 3 T1g(P) 3 A2g→ 3 T2g(F) [Cu(L)2(H2O)2] 274 352 36496 28409 2230 731 L.F L.F distorted Oh 1.89 371 26954 484 C.T 722 13850 23 2 Eg→ 2 T2g [Zn(L)2(H2O)2] 274 368 36496 27173 2264 1361 L.F L.F Oh Diamagnetic 406 24630 392 C.T [Cd(L)2(H2O)2] 277 347 36101 28818 2424 406 L.F L.F Oh Diamagnetic 401 24937 171 C.T [Pd(L)2] 302 345 33112 28985 2121 2188 L.F L.F Sp Diamagnetic 380 26315 1231 C.T 719 804 13908 12437 4 2 1 A1g→ 1 B1g 1 A1g→ 1 E1g Chemistry |221 https://doi.org/10.30526/30.3.1617 7302(عام 0العدد ) 03مجلة إبن الهيثم للعلوم الصرفة والتطبيقية المجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (3) 2017 Table (4): TGA/DTG data for [Cd(L)2(H2O)2]complex Stable up toºC step Dec. Temp. Initial-Final (ºC) DTG Temp . (ºC) Wt. of mass loss (calc)- found Reaction Total mass loss% Wt. of mass loss (calc)- found % 78 1 78-193 138 (0.6594)-0.5700 - 2H2O (87.912) 88.66 (3.471)-3.000 2 193-319 296 (7.9515)-8.1624 -(CS2+ C14H11N3OS2F3) (41.85)-42.960 3 319-415 383 (5.8387)-5.6335 - (CS2 + C12H8NOF3) (30.73)-29.65 4 415-578 484 (2.2535)-2.4795 - C6H7N2O (11.861)-13.05 residue 578 ≤ - (2.2967)-2.5346 CdO - Table (5): Bacterial activity of ligand and its complexes S. Aureus (G+) B. stubtilis (G+) P. aeruginosa(G−) E. coli (G−) Compounds 16 _ _ 13 NaL 26 26 30 16 [Co(L)2(H2O)2] 29 28 32 15 [Ni(L)2(H2O)2] 22 24 25 17 [Cu(L)2(H2O)2] 23 22 23 18 [Zn(L)2(H2O)2] 22 26 27 17 [Cd(L)2(H2O)2] 22 27 24 15 [Pd(L)2] Chemistry |222 https://doi.org/10.30526/30.3.1617 7302(عام 0العدد ) 03مجلة إبن الهيثم للعلوم الصرفة والتطبيقية المجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (3) 2017 “Figure (1): FTIR spectrum of NaL ligand” “Figure (2): Electronic-spectrum of NaL ligand in DMSO solution” Figure (3): 1 H-NMR-spectrum of NaL ligand in DMSO-d6 Chemistry |223 https://doi.org/10.30526/30.3.1617 7302(عام 0العدد ) 03مجلة إبن الهيثم للعلوم الصرفة والتطبيقية المجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (3) 2017 “Figure (4): 13 C-NMR-spectrum of NaL ligand in DMSO-d6” “Figure (5): Mass-spectrum of NaL ligand” “Figure (6): FTIR-spectrum of [Co(L)2(H2O)2] complex” Chemistry |224 https://doi.org/10.30526/30.3.1617 7302(عام 0العدد ) 03مجلة إبن الهيثم للعلوم الصرفة والتطبيقية المجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (3) 2017 “Figure (7): FTIR-spectrum of [Ni(L)2(H2O)2] complex” “Figure(8): Electronic spectrum of [Pd(L)2] in DMSO solution” “Figure(9): TGA for [Cd(L)2(H2O)2]complex in helium atmosphere” Chemistry |225 https://doi.org/10.30526/30.3.1617 7302(عام 0العدد ) 03مجلة إبن الهيثم للعلوم الصرفة والتطبيقية المجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (3) 2017 Scheme(1) :Synthesis route of NaL ligand Chemistry |226 https://doi.org/10.30526/30.3.1617 7302(عام 0العدد ) 03مجلة إبن الهيثم للعلوم الصرفة والتطبيقية المجلد Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 30 (3) 2017 Scheme (2): Synthesis route of NaL complexes