METAL LIGAND COMPLEXEs - Shodhganga

90 (A) LH ML2 90 (B) ML2

FM FM LH ML
ML
% Species % Species 60 LH2
60
30 MLH
LH2
30

MLH

0 0
3.0 4.5 6.0 7.5 3.0 4.5 6.0 7.5

pH pH

90 (C) LH ML2 90 (D) ML ML2
ML
FM FM LH
% Species 60 % Species 60

MLH MLH
30 LH2 30

0 LH2 6.0 7.5
3.0 4.5 6.0 7.5 0

pH 3.0 4.5

pH

90 (E) 90 (F) ML

FM ML ML2 ML2
LH
60 FM LH
60
% Species % Species
LH2 MLH MLH
30 30

LH2

0 0
3.0 4.5 6.0 7.5 3.0 4.5 6.0 7.5

pH pH

Fig. 4.12: Distribution diagrams of Cu-proline in PG-water mixtures.
% v/v: (A) 10.0, (B) 20.0, (C) 30.0, (D) 40.0, (E) 50.0 and (F)
60.0.

159

90 (A) LH 100 (B) LH
FM
60 FM
75 ML2

% Species ML2 % Species FL
ML
9
30 LH2 MLH 50 ML
25 LH2 MLH
0 6 FL
3 0 6
pH 9 3
pH

100 (C) LH 100 (D) LH
FM
75 FM ML2
ML
50 75 FL
6 9
% Species 25 ML2 % Species 50 ML
LH2 pH 25 LH2
FL
0 9 MLH
3
0 6
3
pH

100 (E) LH ML2 100 (F) LH

FM 75 FM ML2

75

% Species 50 ML % Species 50 MLH ML
FL 25 LH2 FL
LH2
25 MLH

00

36 9 36 9

pH pH

Fig. 4.13: Distribution diagrams of Co-valine in PG-water mixtures. %
v/v: (A) 10.0, (B) 20.0, (C) 30.0, (D) 40.0, (E) 50.0 and (F)
60.0.

160

90 (A) ML2 90 (B)
ML
LH FM LH ML2
FL 60 MLH ML
% Species 60 9 % Species
FM

MLH

30 6 30 6 FL
9
LH2 pH LH2 pH

0 0
3 3

90 (C) 90 (D) MLH ML2
ML
LH ML2

% Species 60 MLH % Species LH
ML 60

LH2

FM 30
30 FM

LH2 FL

0 6 9 0 6 FL
3 3 9
pH pH

90 (E) MLH ML2 100 (F) MLH
ML LH
LH 75 ML2
% Species 60 % Species LH2 ML

LH2 50

30 25 FM
FM

0 6 FL 0 6 9
3 9 3
pH pH

Fig. 4.14: Distribution diagrams of Ni-valine in PG-water mixtures. %
v/v: (A) 10.0, (B) 20.0, (C) 30.0, (D) 40.0, (E) 50.0 and (F)
60.0.

161

80 (A) 80 (B) ML ML2
6
FM LH ML 60 FM LH
60 LH2 ML2

% Species 40 % Species 40
MLH MLH

20 20
LH2
0 6
24 0
4
pH
pH

90 (C) ML2 80 (D) ML ML2
LH
% Species MLH % Species 60 LH
ML MLH
60
40 FM
30 LH2
FM LH2
20

0 46 0
2 246
pH
pH

80 (E) ML ML2 90 (F) ML2
LH
60 LH2 LH2 ML
% Species MLH % Species 60 MLH LH

40 FM

30 FM

20

0 0
246 246

pH pH

Fig. 4.15: Distribution diagrams of Cu-valine in PG-water mixtures.
% v/v: (A) 10.0, (B) 20.0, (C) 30.0, (D) 40.0, (E) 50.0 and (F)

60.0.

162

90 (A) LH 80 (B) LH
MLH
% Species MLH ML2 % Species 60 FM ML2
60 ML 40 ML

FM 6 9 20 LH2 6 9
30
pH 0 pH
LH2 3

0
3

80 (C) LH ML 90 (D) MLH LH ML2
MLH 2 ML
60 60
ML 9
% Species % Species
40
FM

20 30 LH2
LH2 FM

0 6 0 6 9
3 3
pH pH

90 (E) MLH 90 (F) MLH
LH
ML2 LH ML2
ML
% Species 60 ML % Species 60

30 LH2 30 LH2
FM FM

0 6 9 0
3 369
pH
pH

Fig. 4.16: Distribution diagrams of Co-proline in AN-water mixtures.
% v/v: (A) 10.0, (B) 20.0, (C) 30.0, (D) 40.0, (E) 50.0 and (F)
60.0.

163

% Species 90 (A) MLH LH 80 (B) LH ML2
ML2 MLH ML
60 60
ML 6 9
40
30 LH2 % Species FM pH
FM
20 LH
0 6 9 2
3
pH 0
3

90 (C) MLH 90 (D) MLH
LH
60 ML2 ML2
ML
% Species % Species 60 LH ML
9
30 LH2 LH2
30
FM
FM
0
3 6 9 0 6
3
pH pH

100 (E) MLH 90 (F)

LH ML2 MLH ML2
ML LH2
LH ML
75
% Species LH2 % Species 60

50

25 30 FM
FM

0 6 9 0 6 9
3 3
pH pH

Fig. 4.17: Distribution diagrams of Ni-proline in AN-water mixtures.
% v/v: (A) 10.0, (B) 20.0, (C) 30.0, (D) 40.0, (E) 50.0 and (F)
60.0.

164

90 (A) LH ML2 90 (B) LH ML2
FM ML
60 FM ML
60
% Species % Species
30 MLH 30 LH2
MLH
LH2
0 6 8 0
468
4
pH
pH

90 (C) ML2 90 (D) LH ML ML2
ML
FM LH FM
60
% Species % Species 60 LH2

MLH MLH
30 30

LH2

0 0
468
4 pH 6 8
pH

90 (E) ML ML2 90 (F) ML ML2

% Species FM LH % Species 60 LH
60 LH2
MLH MLH
30 30 FM

LH2

0 0

4 pH 6 8 4 pH 6 8

Fig. 4.18: Distribution diagrams of Cu-proline in AN-water mixtures.
% v/v: (A) 10.0, (B) 20.0, (C) 30.0, (D) 40.0, (E) 50.0 and (F)
60.0.

165

90 (A) LH 90 (B) LH
FM
FM 60
% Species % Species ML ML2
60

30 MLH ML ML2 30 LH2 MLH
9
LH2 6 0 6 9
ML ML2 3 ML2
0 pH pH ML
3 90 (D)
LH
90 (C) LH 60 FM
FM
60
% Species % Species
30 LH2 MLH 30 LH2
MLH

0 6 0 6 9
3 93
pH
pH

(E) LH ML2 (F) LH
FM ML
90 90 ML2
% Species 60 % Species 60 FM

ML

LH2 MLH
30 MLH 30

LH2

00

369 369

pH pH

Fig. 4.19: Distribution diagrams of Co-valine in AN-water mixtures. %
v/v: (A) 10.0, (B) 20.0, (C) 30.0, (D) 40.0, (E) 50.0 and (F)

60.0.

166

90 (A) LH ML2 90 (B) LH ML2

% Species 60 FM ML % Species 60 FM
MLH
MLH ML
30
30
6 9 LH2 6 9
LH2
pH 0 pH
0 3
3

90 (C) LH ML2 90 (D) LH ML2
9
% Species FM ML % Species 60 MLH ML
60
FM
MLH
30
30 LH2
LH2

0 6 0 6 9
3 3
pH
pH

90 (E) LH ML2 90 (F) LH ML2

% Species 60 MLH ML % Species MLH ML
60

FM FM
30
30
LH2 LH2

00
3 6 93 6 9

pH pH

Fig. 4.20: Distribution diagrams of Ni-valine in AN-water mixtures. %
v/v: (A) 10.0, (B) 20.0, (C) 30.0, (D) 40.0, (E) 50.0 and (F)
60.0.

167

90 (A) LH ML 90 (B) ML
ML2 ML2
FM FM LH

% Species 60 LH2 % Species 60 LH2

30 MLH MLH
30

0 6 0 6
24 ML2 3 ML2

pH 6 pH
ML2
80 (C) ML 80 (D) ML
LH
60 LH 60 FM
FM
% Species % Species
40 40
MLH LH2

20 LH2 20 MLH

0 0 6
4 4 ML2

pH pH

% Species 80 (E) ML % Species 90 (F) ML

60 LH2 LH LH2 FM
40 MLH 60 LH
20
FM 30 MLH

0 6 0 6
4 4

pH pH

Fig. 4.21: Distribution diagrams of Cu-valine in AN-water mixtures.
% v/v: (A) 10.0, (B) 20.0, (C) 30.0, (D) 40.0, (E) 50.0 and (F)
60.0.

168

Structures of binary complexes
Although it is not possible to elucidate or confirm the structures

of complex species pH metrically, they can be proposed based on the
literature reports and chemical knowledge. In aqueous solutions metal
ions are coordinated by six water molecules. Amino acids replace
water molecules and form metal-amino acid complexes60-63.
Depending upon the nature of the ligands and metal ions and based
on the basic chemical knowledge tentative structures of the complexes
are proposed as shown in Figs. 4.22 and 4.23 for proline and valine
complexes. Carboxyl oxygen and amino nitrogen of ligands are bonded
to the metal ions. Amino nitrogen can associate with hydrogen ions in
physiological pH ranges and it results in the formation of protonated
species. Hence protonated complex species are detected in the present
study. The Cu(II) ion forms distorted octahedral or square planar
complexes due to Jahn-Teller effect.

169

S S S S
S S NH
NH2
M M
S
SO O O O
S S
M
MLH2+ O ML+

O

NH

NH O O
S

ML2
Fig. 4.22: Proposed structures of L-proline complexes, where S is

either solvent or water molecule.

O O

NH3

O S O H2
S S N

M M

SS SS
S S

MLH2+ ML+
O

O H2
S N

M

NS
H2 O

O ML2

Fig. 4.23: Proposed structures of L-valine complexes, where S is
either solvent or water molecule.
170

REFERENCES

1. Thomas G., Medicinal Chemistry, John Wiley and Son Co. Ltd.,
London, 2002.

2. Louie A. Y. and Meade T. J., Chem. Rev., 99, 1999, 2711.
3. Patel R. N., Singh N., Shukla K., Chauhan U. K., Chakraborty

S., Gutierrez J. N. and Castineiras A., J. Inorg. Biochem., 98,
2004, 231.
4. Fairlamb A. H., Henderson G. B. and Cerami A., Proc. Natl.
Acad. Sci., U.S.A, 86, 1989, 2607.
5. Balcarova Z., Kasparakova J., Zakovska A., Novakova O., Sivo
M. F., Natile G. and Brabek V., Mol. Pharmacol., 53, 1998, 846.
6. Lafemina R. L., J. Virol., 66, 1992, 7414.
7. Moore P. S. and Jones C. J., Biochem. J., 307, 1995, 129.
8. Rixe O., Ortuzar W., Alvarez M., Parker R., Reed E., Paull K. and
Fojo T., Biochem. Pharmacol., 52, 1996, 1855.
9. Bakhtiar R. and Ochiai E. I., Gen. Pharmacol., 32, 1999, 525.
10. Hammud H. H., Nemer G., Sawma W., Touma J., Barnabe P.,
Mouglabey Y. B., Ghannoum A., El-Hajjar J. and Usta J., Chem.
Biol. Interact., 173, 2008, 84.
11. Liu J., Dabrah T. T., Matson J. A., Klohr S. E., Vol K. J., Kerns
E. H. and Lee M., J. Pharm. Biomed. Anal., 16, 1997, 207.
12. Guebitz G., Pierer B. and Wendelin W., Chirality, 4, 1992, 333.

171

13. Bjerrum J., Metal ammine formation in aqueous solution, Hasse
P. and Son, Copenhagen, Kgl Danske, Videnskab, 22, 1945,
1773.

14. Bjerrum J., Schwarzenbach G. and Sillen L. G., Stability
constants of metal ion complexes, 17, 1964, 7; Special
publication No. 25, 1971, 8.

15. Martelll A. E. and Smith R. M., Ctritical Stability constants of
Inorganic Complexes, Plenum Press, New York, 4, 1976.

16. Irani R. R. and Callis C. F., J. Phys. Chem., 65, 1961, 934.
17. Irani R. R., J. Phys. Chem., 65, 1961, 1463.
18. Calvin M. and Wilson K. W., J. Am. Chem. Soc., 67, 1945, 2003.
19. Calvin M. and Melchior N. C., J. Am. Chem. Soc., 70, 1948,

3270.
20. Busse H. G. and Maass G., Z. Phys. Chem., 66, 1969, 92.
21. Zarrinpar, Park S. H. and Lim W. A., Nature, 426, 2003, 676.
22. Mathew S. P., Iwamura H. and Blackmond D. G., Angew. Chem.

Int. Ed., 43, 2004, 3317.
23. Sketty K., Process Biochem., 39, 2004, 789.
24. Durrani A., Rasayan J. Chem., 4, 2011, 554.
25. Morzyk B. and Zelichowicz N., Chem. Papers, 46, 1992, 84.
26. Ammar R. A., Al-Mutiri E. M. and Abdalla M. A., Fluid Phase

Equilibria, 301, 2011, 51.
27. Tanaka M. and Tabata M., Bull. Chem. Soc. Jpn., 82, 2009,

1258.

172