1. Synthesis and Characterization of [2-(carboxy methylene-amino)- phenyl imino] acetic acid (L) and its some metal complexes Dr. Jasim Shihab. Sultan*, prof. Dr.Falih Hussan. Mosa* Department of Chemistry, College of Education, Ibn-Haitham, University of Baghdad. * Email: ja.sultan@yahoo.com. ja.sultan@yahoo.com Address to * Email: drfalihhassan@yahoo.com.

2. N- substituted imines, also known as Schiff bases, have been used extensively as ligands in the field of coordination chemistry, furthermore the Schiff bases are very important tools for the inorganic chemists as these are widely used to design molecular ferromagnets, in catalysis, in biological modeling applications, as liquid crystals and as heterogeneous catalysts. Glyoxilic acid and its derivatives play important roles in natural processes, participating in glyoxylate cycle which functions in plants and in some microorganisms. Physical- chemical study of complexation of glyoxilic acid aroyl hydrazones with Cu(I) in solution and solid phase is reported. Introduction

3. Instrumentation 1. FTIR spectra were recorded in KBr on Shimadzu- 8300 Spectrophotometer in the range of (4000-400 cm –1 ). 2. The electronic spectra in H 2 O were recorded using the UV-Visible spectrophotometer type (spectra 190-900 nm) CECIL, England, with quartz cell of (1 cm) path length. 3. The melting point was recorded on "Gallen kamp Melting point Apparatus". 4. The Conductance Measurements were recorded on W. T. W. conductivity Meter. 5. Metal analysis. The metal contents of the complexes were determined by atomic absorption (A. A.) technique. Using a shimadzu PR-5. ORAPHIC PRINTER atomic obsorption spectrophotometer. 6. Balance Magnetic Susceptibility model MSB-MLI Al-Nahrain University 7. The characterize of new ligand (L) is achieved by: A: 1 H and 13 C-NMR spectra were recorded by using a bruker 300 MHZ (Switzerland). Chemical Shift of all 1 H and 13 C-NMR spectra were recorded in  (ppm) unit downfield from internal reference tetramethylsilane (TMS), using D2O as a solvent. B: Elemental analysis for carbon, hydrogen for ligand and its complexes were using a Euro Vector EA 3000 A Elemental Analysis (Italy). C: These analysis (A and B) were done in at AL-al-Bayt University, Al- Mafrag, Jordan.

4. 1. Ligand Synthesis Solubility Found (Calc.) %  effect Colour M.P. C  Yield % Empirical formula metalNHC Water, methanol, ethanol, ether, acetone, DMF, DMSO - (13.06) 12.72 (3.64) 3.63 (54.60) 54.54 - Light brown 17086L=C 10 H 8 N 2 O 4 Synthesis Table (1): The physical properties for synthesized lignad (L)

5. Table (2a): 1 H-NMR Chemical Shifts for Ligand (L) (ppm in D 2 O) COOHHC=N Undeurated DMSO Water in DMSO WaterAromatic protons 12.5 ppm8.20 ppm2.5 ppm3.5 ppm5.2 ppm7.37-7.79 ppm Fig. (1): The 1 H-NMR spectrum of the ligand (L)

6. Hc =NCOOHAromatic carbons 159 ppm170 ppm110-130 ppm Table (2b): 13 C-NMR Chemical Shifts for Ligand (L) ( ppm in D 2 O) Fig. (2): The 13 C-NMR spectrum of the ligand (L)

7. Table (3): Infrared spectral data (wave number  – ) cm –1 for the ligand and precursors  symm. COO –  assm. COO –  (C=O)  (C-H) Aromatic  (C=N)  (NH 2 )  (OH) Compound 17453361Glyoxylicacid 30573387 3363 o-phenylenc diamine 1373154116993118 3000 1683L=C 10 H 8 N 2 O 4 Fig. (3): The IR spectrum of the ligand (L)

8. Table (4): Electronic spectral data of the Ligand (L) Assignments (  max molar –1 cm –1 )  – wave number cm –1  nm Compound n  *  * 409 2347 29411 43859 340 229 L=C 10 H 8 N 2 O 4 Fig. (4): Electronic spectrum of the ligand (L)

9. 2. Synthesis of complexes

10. Solubility Found (Calc.) %  effect Colour M.P. C  Yield % Empirical formula metalNHC Water, methanol, ethanol, cetone DMF, DMSO (18.20) 18.84 (9.21) 8.94 (3.61) 3.19 (37.61) 38.09 4.90 Dark green 17090] [LCo.2H 2 O = (18.31) 18.84) (8.91) 8.94 (3.61) 3.19 (37.63) 38.09 3.20 Pale brown 120 D  92[LNi.2H 2 O] = (30.11) 30.60 (7.62) 7.65 (2.09) 2.73 (36.84) 37.85 1.90 Redish brown 15088[LCu].3H 2 O = (30.11) 30.60 (7.62) 7.65 (2.09) 2.73 (32.00) 32.78 - Pale brown 240D  80[LCd.2H 2 O] = (44.80) 44.11 (6.76) 6.16 (2.25) 2.20 (26.68) 26.43 - Pale brown 14082[LHg.2H 2 O] = (44.20) 44.90 (6.61) 6.07 (1.86) 1.30 (25.71) 26.03 - Pale brown 23085[LPb.2H 2 O] Table (5): The physical properties for complexes

11. M-OM-N Coordinate water  cm –1  symm. COO –  assm. COO –  (C=O)  (C-H) Aromatic  (C=N)  (OH) Compound 4245118941581396155416603188 3014 16143163 [LCo.2H 2 O] 4595118941461400154616353100 3010 16353363 [LNi.2H 2 O] 4405208961871390157716743057 3020 16373182 [LCu].3H 2 O 4264899141461388159016143109 3100 16143120 [LCd.2H 2 O] 4245169791601386154616123122 304716123122 [LHg.2H 2 O] 4245409021621384154616203124 3059 16203124 [LPb.2H 2 O] Table (6): Infrared spectral data (wave number  – ) cm –1 for complexes

12. Fig. (5): The IR spectrum of the [LNi.2H 2 O] complex Table (7): Electronic spectral data for complexes Proposed structure Assignments (  max molar –1 cm –1 )  – wave number cm –1 nm Compound Octahedral 4 T 1 g (P)  4 T 1 g 3825 3505 21645 20.618 462 485 [LCo.2H 2 O] Octahedral 3 T 1 g (F)  3 A 2 g (F) 3 T 1 g (P)  3 A 2 g (F) 64 3000 14619 22471 684 445 [LNi.2H 2 O] Square planar 2 A 1 g  2 B 1 g 2 Eg  2 B 1 g 339 3999 12437 21834 804 458 [LCu].3H 2 O OctahedralC. T.66429239342[LCd.2H 2 O] OctahedralC. T.66429239342[LHg.2H 2 O] OctahedralC. T.66429239342[LPb.2H 2 O]

13. Fig. (6): Electronic spectrum of the [LCo.2H 2 O] complex

14. Solutions chemistry Molar ratio as in Fig. (7): Fig. (7): The mole ratio curve of complex [LCu].3H 2 O in solution (1×10 -3 mole. L -1 ) at ( =272.8 nm)

15. Table (8): stability constant and  G for the Ligand (L) complexes GG 1/KLog KK  AmAsCompounds – 43 0.137.76.2×10 7 0.0041.2851.280[LCu].3H 2 O – 42 0.137.42.7×10 7 0.0060.8670.862[LCd.2H 2 O] Table (9): The molar conductance of the complexes ratio  m S.cm 2 molar –1 Compound fragmentations 1:1160[LCo.2H 2 O] 1:1180[LNi.2H 2 O] 1:1130[LCu].3H 2 O 1:1170[LCd.2H 2 O] 1:1135[LHg.2H 2 O] 1:1180[LPb.2H 2 O] Molar conductivity for the complexes of the ligand (L)

16. Conclusion The new Schiff (L) and metal complexes where prepared [LCo.2H 2 O], [LNi.2H 2 O], [LCu].3H 2 O. [LCd.2H 2 O], [LHg.2H 2 O] and [LPb.2H 2 O]. The metal (II) ions are coordinated by two carboxylate –O atoms and two imine (H C= N) atoms. Spectroscopic, structurical and magnetic data show that all complexes are six-coordinate metal complexes owing to the ligation of tetradentate Schiff base moieties with two coordinated water except [LCu].3H 2 O showed square planar geometry as fellow: (Octahedral) (Square planar)