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Bangladesh Pharmaceutical Journal 17(1): 46-50, 2014

Synthesis, Characterization and Antibacterial Activity of
Mixed Ligand Complexes of Pd(II) Ions with Oxalic Acid and
Heterocyclic Amines
Md. Belayet Hossain1, Md. Abdus Salam2, Farzana Siddiquee1 and M. A. Yousuf1
1

Department of Chemistry, Khulna University of Engineering & Technology, Khulna-9203, Bangladesh
2

Department of Chemistry, University of Dhaka, Dhaka-1000, Bangladesh

Abstract
The present work has been designed for the characterization and antibacterial studies of mixed ligand complexes of
Pd(II) ions with phthalic acid and heterocyclic amines. The general formula of the complexes is (MLL) [where, M
= Pd(II); L = Oxalic acid, C2O4, L = Quinoline, C9H7N(1); iso-Quinoline, C9H7N(2)]. The complexes were
prepared in the solid form and characterized by elemental analysis, conductivity & magnetic measurements and
infrared & electronic spectroscopic studies. The infrared spectra of the complexes confirmed the coordination of
metal ion with ligands. Their antibacterial activity has been evaluated by the disc diffusion method against seven
pathogenic bacteria (three gram positive and four gram negative). The complexes were shown to exhibit mild to
moderate antibacterial activity against the tested bacteria.
Key words: Pt(IV) complexes, oxalate, antibacterial activity.

Introduction
Mixed ligand complexes with metal ion bound to two
different and biochemically important ligands have gained
interest as model for metallo-enzymes (Bowen et al.,
2009; Navarro et al., 2010, 2011). The physiologically
interesting mixed ligand complexes of transition metals
with heterocyclic amines play an important role in
biological systems and have been a subject of great
interest for researchers (Reza et al., 2003; Hossain et al.,
2012). Platinum(II) complexes and its derivatives have
been widely recognized as potent anticancer agents,
effective against different types of cancer in vitro (Lin et
al., 2011; Neves et al., 2010). After the discovery of its
activity, thousands of platinum complexes have been
synthesized and tested so far. In a recent study, new Pt
based agents have been reported to have distinct features
from marketed platinum drugs in several critical aspects
(Gao et al., 2009). Cisplatin has become a standard drug
for the treatment of patients with non-small cell lung
cancer. However, it is one of the most frequently used
chemotherapeutic drugs (Lottner et al., 2002; Brow et al.,
2002; Liao et al., 2008). Palladium(II) complexes on the
other hand, have been reported to possess antitumor
activity at least comparable to cisplatin (Gao et al., 2010).
The metal complexes of malonic and succinic acid and

their activities have been reported (Reza et al., 2003;
Islam et al., 2003). All of these experimental works and
evidences prompted us in the formation of dibasic acid
complexes with metal atoms. Keeping these facts in view,
the present work describes some mixed ligand complexes
of palladium (II) with oxalic acid (OXH2) as primary
agents and heterocyclic bases, viz., quinoline (Q), isoquinoline(IQ) as secondary ligands have been prepared
and their antibacterial studies have been performed, which
may help in the primary selection of these complexes as
therapeutic agents.
Materials and Methods
Chemicals and reagents: All the chemicals were of
reagent grade and unless otherwise specified, were used as
received. The solvents were purified using conventional
methods.
Physical measurements: Infrared spectra were
recorded on FTIR spectrophotometer (IR-Prestrige-21) in
the region 4500-400 cm-1 at the Department of Chemistry,
University of Dhaka, Bangladesh. Carbon, hydrogen and
nitrogen analyses were carried out by LECO CHEN-932,
Organic Elemental Analyzer, University Kebangsaan
Malaysia. Metal was determined by weighing as the oxide
produced by direct ignition. The molar conductance of

Correspondence to: M. A. Yousuf, E-mail: <yousuf2716@yahoo.com>.

Islam et al... This diamagnetism was supported by the small negative values obtained for their magnetic susceptibility. 2003. which were shifted to 1610. The in-plane and out of plane ring deformation modes of the heterocyclic amines observed at ~ 520 and ~ 720 cm-1.1 cm-1 in the spectra of all the complexes. Bauer et al. Then 25 ml of an ethanolic solution of heterocyclic amine bases.1 ~ 1379. Department of Fishery. This indicates the coordination of oxalic acid through the carboxylic acid group. The molar conductance were measured in N. The presence of M-N bonding in the complexes is evident for the appearance of M-N modes at 450. The volume of the solution was reduced to 50% and allowed to cool.0 – 460. / Bangladesh Pharmaceutical Journal 17(1): 46-50. and Enterococcus faecalis (Gram positive) were collected from the Fish Inspection & Quality Control Section. Listeria monocytogenes (Gram positive). Melting points were determined using an electrothermal digital melting point apparatus.0 ~ 1610. 1966).81 cm-1 revealed the presence of carboxylic group in oxalic acid due to C=O and C-O.47 Hossain et al..0 cm-1 in the spectra of the complexes (Hossain et al. washed several times with ethanol and then dried a in desiccator over anhydrous CaCl2. e. General methods for complexes preparation: A 25 ml of ethanolic solution of the metal salt (PdCl2) (1 mmole) and oxalic acid (1 mmol) were mixed in the calculated ratio with constant stirring at 70°C. 2003.. which indicated that these complexes were non-electrolyte in nature (Sukalpa et al. Khulna. Islam et al. .0 cm-1 in the spectra of the complexes. University of Dhaka. respectively underwent a positive shift in mixed ligand complexes conforming thereby a co-ordination through nitrogen and presence of M-O bonding is evident from the appearance of M-O modes at 500. Then in vitro anti-bacterial activity of these complexes was assessed by the disc diffusion method (Rios et al. Salmonella bovismorbificans (Gram negative). 1988.5 – 510. Boyra. Islam et al.56 and ~ 1441.40) -1 cm2 mole-1. Magnetic moment: The observed magnetic moment of the complexes at room temperature is given in Table 1. The diameter of the zone of inhibition produced by the complexes was compared with that of Kanamycin (30 g disc-1). It appears from the magnetic moment data that the complexes of Pd(II) ion display diamagnetic property and an square planar geometry with dsp2 hybridization which are consistent with the published structure (Sukalpa et al. 1991).g.Ndimethyl formamide. No precipitate was observed. 2014 10-3 M solutions of the metal complexes in DMF was measured at 30C using a Jenway 4310 Conductivity meter having a dip-cell with platinized electrode. Antimicrobial screening: Seven pathogenic bacteria viz Psudomonas aeruginosa (Gram negative). Escherichia coli (Gram negative). Pd(II) ** ** ** ** 5s 4d 5p 2 dsp hybridization Infrared spectral studies: In the infrared spectra strong bands between ~ 1692.75 – 12. 2004. Magnetic susceptibility was measured with Magnetic Susceptibility Balance (Model: Mk1.. Staphylococcus aureus (Gram positive). England) at the Department of Chemistry. IQ (for complex 2) were added with constant stirring. The precipitate formed was filtered.. All susceptibilities were corrected for diamagnetic contribution using Pascal’s constant (Vogel. Sherwood Scientific. The conductance values of the Pt(IV) complexes were in the range (10.. Bangladesh at 298 °K. 1961). 2004. 2 mmol of Q (for complex 1). Salmonella typhi (Gram negative). The characteristic ring vibration of the heterocyclic amines in the range 1400-1600 cm-1 generally show significant changes on complexation but in our present complexes these bands could not be distinguished because of overlapping with C=O and C-O stretching bands.. The magnetic moment values of the complexes indicated that these complexes are diamagnetic. Hossain et al. The complexes were dissolved separately in acetonitrile to get a concentration of 50-g disc-1.5 cm-1 and 1379. The analytical data are in good agreement with the proposed empirical formula of the present complexes. 1991). Cambridge. Nutrient agar was used as the bacteriological media.. Results and Discussion Elemental analysis and conductivity measurement: The analytical data and their physical properties of the complexes are summarized in Table 1.

41 (23. Psudomonas aeruginosa (-ve) Diameter of zone of inhibition complexes* (mm) 1 2 Kanamycin 30 g/disc 11 23 22 Salmonella bovismorbificans (-ve) S.1A1g 1A2u &1A1g 1Eu respectively.155-28500.12) 6. Table 2.1 510. Complexes (OH) (N-H) (C=O) (C-O) (M-O) (M-N) Pd(OX)(Q) Pd(OX)(IQ)2 - - 1610. 2014 2012a. Q =quinoline.000 28.R. 2003. Results of antibacterial activity of the complexes.0 Table 3. Table 4.5 1610. 35.0 455. spectral data for the complexes are given in Table 2.40 Dia where. Key I. 28.050 * See table 1.0 500.21 (3. Com. 1 2 * See table 1.000-34.500 31.92 (53.89 (53.45 (23.) 270 10.050-31. OX = Diprotonated oxalic acid.19) 6. Table 1.0 1379. 31.51) 52. 1991). A1g 1A2u 28. / Bangladesh Pharmaceutical Journal 17(1): 46-50.05) 3.155 31.115. Dia = Diamagnetic. Electronic spectral data are presented in Table 3.040 1 Spectral band (cm-1) with assignment 1 1 A1g 1B1g A1g 1Eg . kanamycin and results have been presented in Table 4. Electronic spectral data (cm-1) of palladium(II) complexes..1 1379.18 (6.18 (3.220 23.1A1g 1Eg .1A1g 1 B1g .. Com.505 and 40.505 1 A1g 1Eu 40. Electronic spectra: The electronic spectra of the Pd(II) complex in DMSO showed three spin allowed d-d transitions and two charge transfer bands. which indicates square planar stereochemistry (Sukalpa et al.165 40. Infrared spectral data of the complexes (band maxima in cm-1). b). typhi (-ve) 18 16 16 17 22 20 Escherichia coli (-ve) 23 19 20 Listeria monocytogenes (+ve) 31 26 25 Staphylococcus aureus (+ve) 23 22 23 Enterococcus faecalis (+ve) 15 21 21 Test organism *See table 1 .75 Dia 255 12. Com. Islam et al. From the data it may be concluded that our synthesized complexes have shown mild to moderate antibacterial activity. Complex 1 showed the lowest inhibitory zones against Psudomonas aeruginosa corresponding to zone size of 11 mm.48 Hossain et al.51) 23. Elemental analyses and physical properties of the complexes.050 34.13 (6. No. No* 1 1 2 A1g 1A2g 22. IQ= iso-quinoline.115 35.N Complexes o (Colour) 1 2 Yields % Pd(OX)(Q)2 (Yellow) Pd(OX)(IQ)2 (Apricot) 61 65 Metal % Carbon % Hydrogen % Nitrogen % 23.05) 52.5 460.165 cm-1 corresponding to the transitions of 1A1g 1A2g .040. The bands were obtained at 22.12) 3. Antimicrobial activity: The Antibacterial activity of the ligand and its complexes have been studied against various microorganisms (both Gram-positive and Gramnegative bacteria) and the results have been compared with the standard drug.220-23.19) Melting point (± 5C) AM (ohm-1 cm2 mol-1) eff (BM.050-40.

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