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Inorganic Chemistry
ISSN
0975-6299
ABSTRACT
The organic ligands contain nitrogen, oxygen and carbonyl and were used for preparation
of Metal Ligand chelated complexes . An ethanolic solution of salicylaldoxime,
dimethylglyoxime and benzoin were reacted with aqueous solution of metal salts to give
complex with symmetric ligands. Two different ligand solutions were mixed one after other
in aqueous metal salt solution to give asymmetric ligand that is mixed ligand complexes
having general formula [M(S)(D)] & [M(D)(B)] .The resulting product was found to be solid
which have been characterized using FTIR spectrum which shows bands for
characteristic frequencies in which OH,-C=O,-C=N, C-O, M-O and M-N the groups are
present. UV-Vis spectroscopy shows that nitrogen and oxygen of ligands donate the
electron pair to metal and form the cheated complexes. Thermo Gravimetric Analysis
(TGA) of all mixed ligand complexes was carried out to determine the procedural and
decomposition temperatures. The temperature range in which decomposition occurs is in
between 115oC-440oC. The magnetic properties were determined from Gouy balance
method. The eff. was found to be from 3.20 BM to 4.88BM as against the calculated
5.93BM value by using spin only formulae. It indicate that the hybridization of complexes
is sp3d2 having octahedral geometry & is paramagnetic in nature. The complexes were
checked for their biological activity by using E.Coli and B. subtilis bacteria. Only the
mixed ligand complexes of benzoin and Dimethylglyoxime with Mn (II) were found to be
biological active.
KEYWORDS: Mixed ligands, salidox, DMG, Benzoin , Manganese.
S. S. JADHAV
Department of Chemistry, New Arts, commerce and Science College,
Ahmednagar-414401, affiliated to University of Pune, Maharashtra, (INDIA).
*Corresponding author
INTRODUCTION
The coordination chemistry of multidentate
ligands have gained much importance for more
than two decades because of their remarkable
biological activity and novel structural features
.[1-3].In view of this ,we report herein the
synthesis ,structural characterization and
antimicrobial studies of Mn(II) complexes
derived from mixed ligands containing some
nitrogen ,oxygen and carbonyl[4-5]. A good
example of this is the Mn(II) benzoin by the
oxygen, dimethylglyoxime and salicylaldoxime
have nitrogen and oxygen as a donor atom to
give good yield of products with different
geometries[6-7] and these complexes are found
to be potentially biologically active[8]. Thus, in
recent years metal complexes of this
type[Mn(S)(D)]
and
[Mn(D)(B)
shows
remarkable biological activity[9]. The organic
bidentate ligand, is the important class of ligand
in co-ordination chemistry and find extensive
application in different fields[10].The ligand
contains donor atoms like nitrogen ,oxygen and
groups like carbonyl therefore its interaction
with metal ions gives complexes of different
geometries and are found to be potentially
biologically active[11-12]. Several research
papers have been published on synthesis and
characterization of transition metal complexes
with mixed ligands [13]. The literature survey
shows that no work has been done on transition
metal
complexes
of
benzoin
and
dimethylglyoxime, salicylaldoxime and benzoin
with Mn (II). The present work describes the
investigation of mixed ligand complexes and
their characterization [14]. The structure is
determined using analytical techniques like;
FTIR Spectroscopy, UV- visible spectroscopy,
and magnetic susceptibility by Gouy balance
method and decomposition temperature is
measured by thermo gravimetric method [15-18]
Table 1
The physical properties and data of the ligands (S, B, D) with their metal
Sr.
no
Melting
Compound
1
2
S (Salidox)
B (Benzoin)
3
4
D (DMG)
Color
Point 0C
Yield %
White
Whitish
faint brown
White
Grey Brown
610C
1340C
---------
2410C
192d*
----78.64
[Mn(Salidox)22H2O]
[Mn(DMG)22H2O ]
Brown
230d*
57.63
[Mn(Benzoin)4H2O]
Light Brown
>3000C
55.96
[Mn(S)(D)2H2O]
320d*
88.57
[Mn(B)(D)2H2O]
Brownish
metallic
Grey
Dark Brown
2800C
88.52
C
------------
H
-----------
O
---------
N
----------
M
--------
----40.88
(40.68)
29.92
(30.01)
49.47
(49.45)
37.19
(36.98)
----4.36
(4.35)
5.64
(5.62)
28.27
(28.27)
4.54
(4.56)
-----24.75
(23.97)
29.87
(28.97)
5.66
(5.45)
27.02
(27.10)
----13.00
(12.87)
17.44
(17.65)
------11.83
(11.98)
-----16.99
(16.98)
17.10
(17.12)
16.24
(16.23)
15.46
(15.44)
23.10
(23.15)
6.74
(6.71)
13.23
(13.21)
52.06
4.85
(52.07)
(4.05)
d*=Decomposition, B= Benzoin; S= Salicyladoxime (Salidox), D =Dimethylglyoxime (DMG).
Table-2
The characteristic band of IR-absorption band of ligands and their complexes
Sr.
no
1
2
3
4
5
6
7
8
Complexes
S (Salidox)
B(Benzoin)
D (DMG)
[Mn(Salidox)22H2
O]
[Mn(DMG)22H2O]
[Mn(Benzoin)4H2
O]
[Mn(S)(D) 2H2O]
[Mn(B)(D) 2H2O]
O-H
C-H
C=O
C-O
M-N
M-O
3209
3418
3209
---
2974
3061
3033
3050
---1679
----1598
1598
----1693
1425
----1466
----1438
---1278
----1270
---------472
------------585
----
3107
3030
---1645
1425
-----
---1466
--1114
-----453
502
----
---
2986
2976
1632
1698
1598
1450
1435
1450
1122
1143
444
458
544
512
5. Thermal Properties
The thermal decomposition of metal Oxalate
has been the subject of many researches. The
thermal decomposition of metal chelated yet
have been not studied. The thermo gravimetric
data was used to determine the dehydration
and decomposition temperatures (Table.3).The
TG
curves
for
[Mn(Benzoin)4H2O],
[Mn(DMG)22H2O]
,[Mn(Salidox)22H2O],
[Mn(D)(S)2H2O]
and
[Mn(D)(B)2H2O] are
shown in ( Fig.1). During this period of nonisothermal heating, the sample undergoes some
transformation in air atmospheres. The final
product formed in the TGA study of all
complexes is MnO2 [32].
6.Thermogravimetric Analysis of Mn(II)
ligands Complexes
Table.3
Thermal Analysis data of the Mn(II) complexes
Sr.No.
Decomposition stage
Temp. range
C
Stage-1
Stage-2
Stage-3
124-140
180-238
280-345
Weight loss
Found (calcd.)
%
10.18 (10.64)
11.95(12.37)
67.29 (67.44)
Stage-1
115-140
11.07 (11.21)
-2 H2O
Stage-2
Stage-3
162-182
220-280
22.28 (23.13)
59.17 (60.33)
-2 H2O,-1/2 O2
-2N2, 2C2H6
Stage-1
192-263
29.43(29.70)
-2 H2O , 2NO
Stage-2
320-378
40.49(45.49)
-2C7H7
[Mn(D)(S).2H2O]
Stage-1
Stage-2
152-340
380-422
35.47 (37.63)
61.80 (63.69)
--2 H2O,-3NO
-C11H13
[Mn(D)(B).2H2O]
Stage-1
Stage-2
144-240
348-375
15.86 (16.37)
73.56(74.96)
-2 H2O, O2
-2NO,-C16H18
Complexes
[Mn(Benzoin).4H2O]
Decompositio
n
Assignment
-2 H2O
-2H2O
-C12H12
[Mn(DMG)2.2H2O]
3
[Mn(Salidox)2 2H2O]
Residue
Remained
Fond
(Calcd.) %
MnO2
9.95
(10.17)
MnO2
5.33 (7.48)
MnO2
25.08
(29.81)
MnO2
0.57 (0.84)
MnO2
8.67 (10.57)
%Wt.loss
20
40
60
80
100
200
300
400
500
600
700
Temperature C
Figure.1
TG-Curves for Mn(II) Complexes.
7. The Electronic Spectra
UV-Visible spectrum of complexes was
measured in DMF solvent Figure 2. Electronic
spectral data of mixed ligand complex
[Mn(S)(D).2H2O] of shows bands in the range of
309 nm-527nm suggesting the existence of
1.6
1.4
1.2
1.0
0.8
0.6
0.4
0.2
0.0
200
400
600
800
wavelenght,nm
Figure.2
Electronic spectra of Mn (II) mixed ligand complexes of [Mn(S)(D).2H2O]
8. Magnetic Properties
The magnetic moment eff for complexes of
Mn+2 (d5 ) were found to be 5.93 B.M . Which
within the expected spin only values [39].The
lower value of Mn+2 (d5 ) complexes shows 4.88
BM-5.23BM may be due to the no orbital
[Mn(Salidox)22H2O]
[Mn(DMG)22H2O]
[Mn(Benzoin)4H2O]
[Mn(S)(D)2H2O]
[Mn(B)(D)2H2O]
No. of
Electro
n
d
d5
d5
d5
d5
No.
Of
Unpaired
Electron
Electron
Configurati
on
5
5
5
5
5
t32g,
t32g,
t32g,
t32g,
t32g,
eg
e2g
e2g
e2g
e2g
Term
Symbol
S
S6
S6
S6
S6
Orbital
Contribution
NO
NO
NO
NO
NO
eff
Foun
d
5.05
5.23
5.18
3.02
4.88
Calculat
ed
5.93
5.93
5.93
5.93
5.93
Figure.3
Photograph of Antimicrobial Activity of Mn(II) complexes.
1.[ Mn(Benzoin)4H2O]
2. [ Mn(DMG )22H2O ]
H
H2O
H3C
OH2
OH
HO
OH2
CH3
Mn
H3C
N
OH2
CH3
Mn
OH2
OH2
OH2
3.[Mn (Salidox)22H2O]
4.[Mn(DMG)(Salidox)2H2O]
OH2
OH2
H
N
O
Mn
H
N
H3C
O
Mn
N
H
N
H
H3C
OH2
OH2
5.[Mn(DMG)(Benzoin)2H2O] Complex
OH2
H
N
CH3
Mn
N
O
H
CH3
OH2
Figure .4
Suggested structure of the Mn(II) Complexes
CONCLUSION
The mixed ligand complexes of salicylaldoxime,
dimethylglyoxime and Bezoin with the general
formulae [Mn(S)(D)2H2O] & [Mn(D)(B) 2H2O]
are found to be totally new and unreported .
The FTIR of ligand & complexes shows the
nitrogen and oxygen
of ligand atoms to
coordinate with the Mn(II). Also from the UVVisible spectra and Gouy balance method it can
be suggested that the octahedral geometry and
paramagnetic nature of complexes is confirm.
REFERENCES
1.