Synthesis and Characterization Synthesis and Characterization of [2-(carboxy methylene-amino)-of [2-(carboxy methylene-amino)-phenyl imino] acetic acid (L) and phenyl imino] acetic acid (L) and

its some metal complexesits some metal complexes

Dr. Jasim Shihab. Sultan*, prof. Dr.Falih Hussan. Mosa*Dr. Jasim Shihab. Sultan*, prof. Dr.Falih Hussan. Mosa*Department of Chemistry, College of Education, Ibn-Haitham, Department of Chemistry, College of Education, Ibn-Haitham, University of Baghdad.University of Baghdad.* Email: * Email: ja.sultan@yahoo.com..Address to * Email: drfalihhassan@yahoo.com.Address to * Email: drfalihhassan@yahoo.com.

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

Introduction

InstrumentationInstrumentation 1. FTIR spectra were recorded in KBr on Shimadzu- 8300 Spectrophotometer in 1. FTIR spectra were recorded in KBr on Shimadzu- 8300 Spectrophotometer in

the range of (4000-400 cmthe range of (4000-400 cm–1–1).).2. The electronic spectra in H2. The electronic spectra in H22O were recorded using the UV-Visible O were recorded using the UV-Visible

spectrophotometer type (spectra 190-900 nm) CECIL, England, with quartz cell spectrophotometer type (spectra 190-900 nm) CECIL, England, with quartz cell of (1 cm) path length.of (1 cm) path length.

3. The melting point was recorded on "Gallen kamp Melting point Apparatus". 3. The melting point was recorded on "Gallen kamp Melting point Apparatus". 4. The Conductance Measurements were recorded on W. T. W. conductivity 4. The Conductance Measurements were recorded on W. T. W. conductivity

Meter.Meter.5. Metal analysis. The metal contents of the complexes were determined by 5. Metal analysis. The metal contents of the complexes were determined by

atomic absorption (A. A.) technique. Using a shimadzu PR-5. ORAPHIC atomic absorption (A. A.) technique. Using a shimadzu PR-5. ORAPHIC PRINTER atomic obsorption spectrophotometer.PRINTER atomic obsorption spectrophotometer.

6. Balance Magnetic Susceptibility model MSB-MLI Al-Nahrain University6. Balance Magnetic Susceptibility model MSB-MLI Al-Nahrain University7. The characterize of new ligand (L) is achieved by:7. The characterize of new ligand (L) is achieved by:A: A: 11H and H and 1313C-NMR spectra were recorded by using a bruker 300 MHZ C-NMR spectra were recorded by using a bruker 300 MHZ

(Switzerland). Chemical Shift of all (Switzerland). Chemical Shift of all 11H and H and 1313C-NMR spectra were recorded in C-NMR spectra were recorded in (ppm) unit downfield from internal reference tetramethylsilane (TMS), using (ppm) unit downfield from internal reference tetramethylsilane (TMS), using D2O as D2O as a solvent. a solvent.

B: Elemental analysis for carbon, hydrogen for ligand and its complexes were B: Elemental analysis for carbon, hydrogen for ligand and its complexes were using a Euro Vector EA 3000 A Elemental Analysis (Italy). 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, C: These analysis (A and B) were done in at AL-al-Bayt University, Al- Mafrag, Jordan.Jordan.

1. Ligand Synthesis1. Ligand Synthesis

Empiricalformula

Yield% M.P. CColoureffect

Found(Calc% ).

Solubility

CHNmetal

L=C10H8N2O486170 Light brown

-(54.60 )

54.54(3.64 )

3.63(13.06 )

12.72-

Water, methanol, ethanol, ether,

acetone, DMF, DMSO

Synthesis

Table (1): The physical properties for synthesized lignad (L)

NH2

NH2

C

O

H

C

O

H

O

2N

N

C

C

H

H

COOH

COOH

2H2OEtOH

Ref. 3.5hr.

1 mmole 2 mmole

Table (2a): 1H-NMR Chemical Shifts for Ligand (L) (ppm in D2O)

Aromatic protonsWaterWater in DMSO

Undeurated DMSO

HC=NCOOH

7.37-7.79 ppm5.2 ppm3.5 ppm2.5 ppm8.20 ppm12.5 ppm

Fig. (1): The 1H-NMR spectrum of the ligand (L)

Aromatic carbonsCOOHHc =N

110-130 ppm170 ppm159 ppm

Table (2b): 13C-NMR Chemical Shifts for Ligand (L) ( ppm in D2O)

Fig. (2): The 13C-NMR spectrum of the ligand (L)

Table (3): Infrared spectral data (wave number –) cm–1 for the ligand and precursors

Compound)OH()NH2()C=N()C-H(

Aromatic)C=O(

assm.

COO–

symm.

COO–

Glyoxylicacid33611745

o-phenylenc diamine

33873363

3057

L=C10H8N2O4168331183000

169915411373

Fig. (3): The IR spectrum of the ligand (L)

Table (4): Electronic spectral data of the Ligand (L)

Compound nm– wave number

cm–1) max molar–1 cm–1(Assignments

L=C10H8N2O4340229

2941143859

4092347

n*

*

Fig. (4): Electronic spectrum of the ligand (L)

2 .Synthesis of complexes

N

N

C

C

H

H

COOH

COOH

MX2

1 mmole

EtOH

NN CCH H

CC OO M

O OH2O

H2O

OrNN CCH H

CC OO Cu

O O

. 3H2O

[LM.2H2O] [LCu].3H2O]

where MII = Co, Ni, Cd, Hg, Pb

1 mmole

Empiricalformula

Yield% M.P. C

Coloureffect

Found(Calc% ).

Solubility

CHNmetal

[ ]LCo.2H2O90170Dark green

4.90)37.61( 38.09

(3.61)3.19

(9.21)8.94

(18.20)18.84

Water, methanol, ethanol,

cetone DMF, DMSO

[LNi.2H2O]92120 DPale brown

3.20(37.63)

38.09(3.61)

3.19(8.91)

8.94(18.31)

18.84(=

[LCu.]3H2O88150Redish brown

1.90(36.84)

37.85(2.09)

2.73(7.62)

7.65(30.11)

30.60=

[LCd.2H2O]80240D Pale brown

-(32.00)

32.78(2.09)

2.73(7.62)

7.65(30.11)

30.60=

[LHg.2H2O]82140Pale

brown-

(26.68)26.43

(2.25)2.20

(6.76)6.16

(44.80)44.11

=

[LPb.2H2O]85230Pale

brown-

(25.71)26.03

(1.86)1.30

(6.61)6.07

(44.20)44.90

=

Table (5): The physical properties for complexes

Compound)OH()C=N()C-H(

Aromatic)C=O(

assm.

COO–

symm.

COO–

cm–1

Coordinate water

M-NM-O

]LCo.2H2O[3163161431883014

166015541396158894511424

]LNi.2H2 O[3363163531003010

163515461400146894511459

]LCu[.3H2O318216373057

3020167415771390187896520440

]LCd.2H2O[3120161431093100

161415901388146914489426

]LHg.2H2O[312216123122 3047161215461386160979516424

]LPb.2H2O[3124162031243059

162015461384162902540424

Table (6): Infrared spectral data (wave number –) cm–1 for complexes

Fig. (5): The IR spectrum of the [LNi.2H2O] complex

Table (7): Electronic spectral data for complexes

Compoundnm– wave number

cm–1)max molar–1 cm–1(Assignments

Proposed structure

]LCo.2H2O[462485

2164520.618

38253505

4T1g)P(4T1gOctahedral

]LNi.2H2 O[684445

1461922471

643000

3T1g)F(3A2g)F(

3T1g)P(3A2g)F(

Octahedral

]LCu[.3H2O804458

1243721834

3393999

2A1g2B1g2Eg2B1g

Square planar

]LCd.2H2O[34229239664C. T.Octahedral

]LHg.2H2O[34229239664C. T.Octahedral

]LPb.2H2O[34229239664C. T.Octahedral

Fig. (6): Electronic spectrum of the [LCo.2H2O] complex

Solutions chemistry

Molar ratio as in Fig. (7):

0.0 0.5 1.0 1.5 2.0 2.5Volum e of ligand in m l

0.8

0.9

1.0

1.1

1.2

1.3

Abs

Fig. (7): The mole ratio curve of complex [LCu].3H2O in solution (1×10-3 mole. L-1) at (=272.8 nm)

Table (8): stability constant and G for the Ligand (L) complexes

CompoundsAsAmKLog K1/KG

]LCu[.3H2O1.2801.2850.0046.2×1077.70.13–43

]LCd.2H2O[0.8620.8670.0062.7×1077.40.13–42

Table (9): The molar conductance of the complexes

Compound fragmentationsm S.cm2 molar–1ratio

[LCo.2H2O]1601:1

[LNi.2H2 O]1801:1

[LCu.]3H2O1301:1

[LCd.2H2O]1701:1

[LHg.2H2O]1351:1

[LPb.2H2O]1801:1

Molar conductivity for the complexes of the ligand (L)

Conclusion

The new Schiff (L) and metal complexes where prepared [LCo.2H2O], [LNi.2H2O], [LCu].3H2O. [LCd.2H2O], [LHg.2H2O] and [LPb.2H2O]. 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].3H2O showed square planar geometry as fellow:

NN CCH H

CC OO M

O OH2O

H2ONN CCH H

CC OO Cu

O O

. 3H2O

[LM.2H2O] [LCu].3H2O]

where MII = Co, Ni, Cd, Hg, Pb

(Octahedral) (Square planar)