Preparation, Spectroscopic of the new complexes with ... · 3-hedr oxy phenol 4,4'-Bis( 3- hydroxy...

International Journal of Engineering & Technology IJET-IJENS Vol:14 No:01 1

130206-1401-7474-IJET-IJENS © February 2014 IJENS I J E N S

Preparation, Spectroscopic of the new complexes with

ligand 4,4'-Bis( 3- hydroxy phenol azo )- O-tolidine Ahmed Hussein Muhammed, Eman Hassan Sahap, Hawraa Mehdi Farhan and WaleedMuhsenSarhan

Dep. of chemistry, college of science/Un. of Kufa

Abstract-- new Fe(III), Co(III) metal complexes were

synthesize with aryl azo 4,4'-Bis( 3- hydroxy phenol azo )- O-

tolidine [BHPAT] derived from O-tolidine and resorcinol. The

ligand and it’s complexes were characterized by H1NMR, FTIR,

UV-Vis. spectra and conductivity measurements, The ligand

behaves as bidentate (N,O) of the ligand forming chelates with

(2:1) (metal:ligand). The molar conductance values of the Fe(III)

and Co(III) complexes of the bidentate ligand indicate their non-

ionic character, Octahedral environment is suggested for metal

complexes.

Index Term-- Azo, O-tolidine , resorcinol, complex Fe(III) and

complex Co(III)

INTRODUCTION Azo dyes are important class of organic colorants consists

of at least a conjugated chromospheres azo (-N=N-) group and

largest and most versatile class of dyes. There may be more

than one azo group present in the dye molecules and thus

classified into mono azo[1-3] , diazo and poly azo according

to the number azo group in the dye molecules[4,5]. Azo

compounds containing hetroaryl ring systems can form

varieties of metal complexes with transition metal ion as

chelating agent Synthesis azo compounds were widely used

in different fields ,such as dyeing industry[6], Inhibition of

aluminum corrosion[7] polymerization[8,9],biological

activity[ 10],and study effect it on the Ach enzyme .This paper

describe the synthesis and characterization of a new bisazo

ligand and some of its transition metal complexes.

EXPERIMENTAL

Apparatus and materials All the reagents and solvents were of reagent-grade quality

and purchased from commercial suppliers .The Melting points

were determined on aElectrothermal melting point,

GOWLLANDS, England. H MNR spectrum solvent (DMSO)

(400 MHz), IR spectra were recorded using KBr discs 4000-

400 cm-1 on FTIR Test scan Shimadzu model 8400S.while

the UV-Vis. Spectra were recorded in ethanol on Shimadzu

model 1800 . Molar conductance measurements were

determined in ethanol by using a Alpha Digital conductivity

meter model 800 . H1NMR spectrum was taken using

(BRUKER) using (DMSO) as the solvent and SF(400Mz).

Preparation of ligand (BHPAT)

Ligand was prepared according to the following general

procedure [11]. The procedure was seen in Schem.(1) (0.212

gm, 0.001 mole ) of O-Tolidine was dissolved in 30ml of

water and using concentrated hydrochloric acid(pH= 5) . The

filtered solution was diazotized below 5ºC with 20ml of

aqueous (0.138 gm, 0.002mol) sodium nitrate. The result

diazonium chloride solution was mixed with 3-hedroxy phenol

(0.22 gm, 0.002mole) dissolved in 50ml alkaline ethanol

cooled below 0ºC. After leaving in the refrigerator for

30minutes. A solution of one molar sodium hydroxide was

used to precipitate the product the pH of the solution should

be maintain at (9–10),A dark brown crystals were precipitated,

and a recrystallization from ethanol was done twice before

using, m.p.123-121 Co The percentage yield 63%..



2 NaNO2 (0-5 Co)

HCl

H2N

NH2

NCl +N

N N+ Cl

OH

HO

OH

HO

N

NN

N

OH

OH

2

NaOH

Diazonium Chlorid

3-hedroxy phenol

4,4'-Bis( 3- hydroxy phenol azo )- O-tolidine

Scheme (1)Preparation of the ligand (BHPAT )

Preparation of the solid complexes An aqueous of the metal salt contains (0.002 mole) of

FeCl3 and Co(NO3)2.6H2O (Oxidation Co(II) to Co(III) by

add 2-3 drops from H2O2) was add gradually with stirring to

the ethanol solution of the ligand (0.001mol at pH ≈ 7). A

solid complexes were obtained, collected by filtration ,washed

by ethanol and water several times and dried .

Characterization of ligand and its complexes

The complexes were insoluble in water but soluble in

DMF, DMSO and EtOH solvents. The ligand was Dark brown

crystals. Table (1) appears some physical properties of the

prepared of the ligand and complexes.

Table I

Physical properties of the ligand and it's complexes

Compound Formula Color Yield(%) M.P(ºC)

BHPAT C26H22N4O4 deep

brown

63 123-121

Fe(III)-

BHPAT

[Fe 2LCl4

(H2O)4]

deep

brown

70 210 dec.>

Co(III)-

BHPAT

[Co 2L(NO3) 4

(H2O)4

Brown-

black

73 .>210

dec.

RESULTS AND DISCUSSION 1H NMR spectrum

The1H NMR spectrum of the ligand (BHPAT) in (DMSO)

and SF(400 MHz) Fig(1). displayed the presence of the broad

singlet signal due to the hydrogen with azo ( toutomerism),

(2.546, 3.335 ppm, to solvent (DMSO))[12], (7.048-7.370

ppm, d, H-Ar)[13,14], (6.582, 6.602 ppm, d, H-O), (4.825

ppm, d, H-N (tout.) ) )[ 15,16], (2.069-2.479ppm, d, H-C)[17],

Scheme (2).



HO

OH

HO

OH

N

N

N

N

OH

O

O

HO

N

NH

HN

N

Scheme 2 : Keto - enol toutomerism in ligand

Fig. 1. HNMR to the ligand (BHPAT)

Molar Conductivity The molar conductance of the complexes as shown in

Table (3) were carried out in ethanol at room temperature , the

values indicate that the complexes are non- electrolytes

nature[18,19],where the values suggest that no anions present

outside the coordination spheres .

molar ratio of the complexes Composition of the complexes were determined by molar ratio

method at fixed concentration for pH =7 at maximum

wavelengths of absorption. method indicated that the ratio of

metal ion to ligand molecules (M:L) was (2:1). The results are

given in Table (II,III) and Fig. (2,3)

Table II

relation between Abs. and molar ratio for Ph=7 and λ max of the complexes.

M:L (10-5 M)

Ab

s. o

f

com

ple

xes

Complex 5.2:1 5.1 5.7:1 5.5 5.52:1 5.51 5.57:1 Fe(III) (411

nm) 0.071 81..0 81..0 810.0 810.. 81300 81.00

Co(III) (411 nm)

0.078

0.239

0.265

0.339

0.282

0.333

0.492



complex Fe(III)

0

0.1

0.2

0.3

0.4

0.5

0.6

0 0.5 1 1.5 2 2.5 3

(L/M)

Ab

s.

Fig. 2. mole ratio of the complex Fe(III)

complex Co(III)

0

0.1

0.2

0.3

0.4

0.5

0.6

0 0.5 1 1.5 2 2.5 3(L/M)

Ab

s.

Fig. 3. mole ratio of the complex Co(III)

Table III

Metal : Ligand ratios ,Stability constant values and Molar Conductivity of the complexes.

Compound pH λ max (nm) Metal :Ligand β Log β Conductivity S.mol-1.cm2

Fe(III)- BHPAT 7 411 2:1 0.133×108 7.123 10

Co(III)- BHPAT 7 411 2:1 1.378×108 8.139 12

Stability constants are obtained spectrophotometricaly by

measuring the absorbance of solutions of ligand and metal

mixture at fixed wavelength λmax and pH values. The degree

of formation of the complexes is obtained according to the

relationship β = (1 – α) / (4α3 c

2), and α = (Am -As)/Am,

where As and Am are the absorbance of the partially and fully

formed complex respectively at optimum

concentration[20,21]. The calculated β and Log β values for

the prepared

IR spectra

The wave numbers of some characteristic bands in the IR

spectra of ligand, The stretching vibration of OH groups at

(3429 cm-1

) and other vibration at (1112-1040 cm-1

)[22,23],

The ν(N═N) stretching vibration appears (symmetrical) at

(1404 -1473 cm-1

) [15], The asymmetrical (N═N) band

usually overlaps with the bands of the aromatic rings hence is

difficult to identify[24-26] in the free ligand spectra,The

infrared band assignments of the ligand complexes of Fe(III),

Co(III) ions (Table4). this band to vanish in the spectra of

complexes [27], The broad band at (3388,3365cm-1

) in of the

ligand complexes of Fe(III), Co(III) ions which assigned to υ(-

OH (stretching)) free Fig.(4,5). about involvement of phenol

group in coordination with metal ions via oxygen group . New

bands in the region (1390 cm-1

) to (N=O) from NO3 group[17]

Fig.(5) and (821cm-1

) to (OH) in group water

coordination[28,29] Fig.(4) These were assigned in the spectra

of metal complexes. These bands were not present in the

spectrum of ligand, and they due to ν(M─N)and υ(M-O)

vibrations respectively . The appearance of these bonds

support the involvement of azomethine and hydroxyl groups

via nitrogen and oxygen atoms in complexation.

Table IV

FTIR to Ligand and ccomplexes

Compound (O-H) coor. (O-H) free (N=N) (N=O) in

NO3

(O-H) in

water

BHPAT 3429 Overlap 1404-1473 ----- ------

BHPAT- Fe ----- 3388 1454 ----- 821

BHPAT- Co ----- 3365 1452 1390 -----



Fig. 4. IR spectrum to O-Tolidine

Fig. 5. IR spectrum to (BHPAT)

Fig. 6. IR spectrum to complex Fe(III)



Fig. 7. IR spectrum to complex Co(III)

Electronic spectra

The electronic spectral data of the ligand and its complexes

were recorded in ethanol and their assignments are listed in(

table 4). The UV-Visible spectrum of the ligand, Fig.(8)

shows absorption peak at (443 nm) and (297 nm) assigned to

(n→π*) and (π→π*) transitions respectively[30,31]. While the

electronic spectra of the complexes Figs.(9,10) exhibited that

The electronic transitions blue shift[32,33] (411nm) to Fe(III)

complex and (411nm) to Co(III) complex.

The λ max of complexes were slightly blue shifted which

arise from the energy change of intense (n→π*) transition of

the conjugated chromophore due the chelation between metal

ions and azo ligand. The complexation of the dye with the

metal ion was responsible for a significant hypochromic shift

at(n→π*) transition region[34-37] Table (V).

Table V

Electronic spectra of the ligand and it's complexes

Compound λ nm λ cm-1

Assignment

BHPAT 444

792

22573.363

33670.034

n→π*

π→π*

BHPAT- Fe 411

907,

788

24330.9

11025.358,

12690.355

Ligand field

d-d transition

BHPAT- Co 411

907,

787

24330.9

11025.358,

12706.48

Ligand field

d-d transition

Fig. 8. UV-Vis. spectrum to BHPAT



Fig. 9. UV-Vis. spectrum to complex Fe(III)

Fig. 10. UV-Vis. spectrum to complex Co(III)



Suggested chemical Structure formula for the complexes

According to these results (FTIR, U.V.-Vis., molar conductivity and mole ratio) the structural formula of prepared complexes

may be proposed in Fig. (11)and Fig.(12)

OH

O

O

HO

N

N

N

N

Fe

Cl

Cl

Cl

Cl

Fe

OH2

H2O

H2O

H2O

Fig. 11. Suggested (BHPAT- Fe(III))

OH

O

O

HO

N

N

N

N

Co

CoN

O

O

O

N

O

O

O

N

O

O

O

N

O

O

O

Fig. 12. Suggested (BHPAT- Co(III))

CONCLUSION

1- prepared ligand coordinate with Fe(III) and CO(III)

from type (bidentate ).

2- Preparation the complexes were (1:2) (ligand :metal)

from results (UV.-Vis, FTIR, molar conductivity and

mole ratio).

3- The electronic transitions blue shift to Fe(III)

complex and Co(III) complex.

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Preparation, Spectroscopic of the new complexes with ... · 3-hedr oxy phenol 4,4'-Bis( 3- hydroxy...

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