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Int. J. Curr.Res.Chem.Pharma.Sci. 2(8): (2015):7–16
© 2015, IJCRCPS. All Rights Reserved 7
INTERNATIONAL JOURNAL OF CURRENT RESEARCH IN
CHEMISTRY AND PHARMACEUTICAL SCIENCES
(p-ISSN: 2348-5213: e-ISSN: 2348-5221)
www.ijcrcps.com
Research Article
SYNTHESIS AND CHARACTERIZATION OF SOME TRANSITION METAL COMPLEXES WITH
A NEW MONODENTATE PHOSPHORUS YIELD AND THEIR ANTIBACTERIAL ACTIVITIES
SEYYED JAVAD SABOUNCHEIA,*
, SOMAYEH NAZARYANI FARDA
, MAHBUBEH POURSHAHBAZA
,
ROYA KARAMIANB
, MOSTAFA ASADBEGYB
A
Faculty of Chemistry, Bu-Ali sina University, Hamedan, 65174, Iran
B
Department of Biology, Faculty of Science, Bu-Ali Sina University, Hamedan 65174, Iran
*Corresponding Author
Abstract
A new monodentate phosphorus yield Ph3P=CHC(O)C6H4-m-Br (L),was synthesized and characterized with elemental analysis as
well as various spectroscopic techniques. The reactions of the title ylide with mercury(II) halides in equimolar ratios using dry
methanol as solvent have yielded [L.HgX2]2 (X= Cl (1), Br (2), I (3)). The reaction of 1 equiv. this ylide with Cd(NO3)2.4H2O in the
same solvent give a polynuclear complex [Cd (L)(NO3)(μ-NO3)]n (4), followed by treatment with 2 equiv. AgNO3 and AgOTf led to
monomeric chelate complexes 5 and 6, respectively. Characterization of the obtained compounds was also performed by
elemental analysis, IR,
1
H,
31
P and
13
C NMR. All DMSO-solved synthesized compounds were subjected to biological evaluation for
their antibacterial against 6 Gram positive and negative bacteria effects by disc diffusion method. Results showed antibacterial
activity for studied metal complexes and suggested their possible application as antibacterial agents.
Keywords: Phosphorus yields, mercury(II) complexes, silver(I) complexes, cadmium(II) complexes, antibacterial activity.
Introduction
The utility of metalated phosphorus ylides in synthetic
chemistry has been well documented (Christau, 1994;
Kolodiazhnyi, 1996). The keto group in the a-keto
stabilized phosphorus ylides cause resonance
delocalization and provide additional stabilization to the
ylide species (Scheme 1). The synthesis of complexes
derived from ylides and Ag(I) began in 1975 by
Yamamoto et al. (Yamamoto and Schmidbaur, 1975).
Other types of ylide complexes of silver(I) have been
reported (Schmidbaur et al., 1973; Schmidbaur et al.,
1974; Schmidbaur and Richer, 1975; Yamamoto and
Schmidbaur, 1975; Schmidbaur and Scherm, 1977;). In
1987 and 1983, Vicente et al. (Vicente et al., 1987;
Vicente et al., 1993) reported the crystal structures of
Ag(I) complexes of phosphorus ylides. The synthesis of
complexes derived from phosphorus ylides and Hg(II)
salts was limited to Hg(II) halides and was started in
1965 by Nesmeyanov et al. (Nesmeyanov et al., 1965).
Weleski et al. (Weleski et al., 1975) in 1975 proposed
a symmetric halide-bridged dimeric structure for Hg(II)
halide complexes, while Kalyanasundari et al.
(Kalyanasundari et al., 1995) in 1995 reported an
asymmetric halide bridged structure. Antimicrobial
resistance is fast becoming a global concern with rapid
promotion in multidrug resistant bacteria (Bennett,
2008). Development of metal complexes are able to
inhibit bacterial growth has been of great interest in
recent years due to their potential use in paints,
kitchenware, school and hospital utensils, etc. Metal
complexes play important roles in many biological
systems (Kamalakannan, and Venkappayya, 2002;
Islam et al., 2002; Agwara et al., 2011). This revival
interest was generated by the discovery of antibacterial
activity of several metal complexes (Saha et al., 2009;
Sabounchei et al., 2013). Although some Hg(II)
complexes are among the most widely used antibacterial
agents, it seem that the assessment of antibacterial
activity of new metal complexes with ligands system is
Int. J. Curr.Res.Chem.Pharma.Sci. 2(8): (2015):7–16
© 2015, IJCRCPS. All Rights Reserved 8
very necessary. In this study, we describe the
preparation, spectroscopic characterization and
antibacterial activities of Hg(II), Cd(II) and
Ag(I)complexes with the title ylide.
Scheme 1. Resonance forms for a ketostabilized phosphorus ylide
Materials and Methods
2.1. Chemicals and Instrumentation
All reactions were performed in air. All other chemicals
were reagent grade and were used without further
purification. Elemental analysis for C, H and N were
performed using a Perkin-Elmer 2400 series analyzer.
IR spectra were recorded on a Shimadzu 435-U-04
spectrophotometer in a region 4000-550 cm
-1
and the
measurements were made by the KBr disk method.
Melting points were measured on a SMP3 apparatus.
Solution-state
1
H,
31
P and
13
C NMR spectra were
recorded on 400 MHz Bruker and 90 MHz Jeol
spectrometer in CDCl3 as solvent at 25 ºC. Chemical
shifts (ppm) are reported according to internal TMS
and external 85% phosphoric acid.
2.2. Synthesis and Characterization
2.2.1. Synthesis of monophosphonium salt
[Ph3PCH2C(O)C6H4-m-Br]Br (S)
Triphenylphosphine (0.262 g, 1 mmol) was dissolved
in 5 ml of acetone and then a solution of 2,3-di
bromoacetophenone (0.277 g, 1 mmol) in the same
solvent (5 ml) was added dropwise to the above
solution. The resulting yellow solution was stirred for 4
h. The solution was concentrated under reduced
pressure to 2 ml, and diethyl ether (20 ml) was added.
The white solid formed was filtered off, washed with
diethyl ether (210 ml) and dried under reduced
pressure. White solid, 0.269 g (50 %), m.p. 82–85
0
C.
Anal. Calc. for C26H21Br2OP: C: 57.81; H: 3.92; Found:
C: 57.98; H: 3.96.; IR (KBr disk) ν: 1676.34(CO) and
859.37 (P
+
-C
-
) cm
–1
.
1
HNMR (CDCl3) δ: 6.34 (d,
2
JPH
=12.18 Hz, 2H, CH2) and 7.26 – 8.58 ppm (m, 19H,
arom.).
2.2.2. Synthesis of monodentate phosphorus ylide
[Ph3P=CHC(O)C6H4-m-Br] (L)
The phosphonium salt (S) (0.533 gr, 1 mmol) was
transferred to an aqueous NaOH (5 %) and stirred at
40°C for 24 h. The white product was obtained,
washed with distilled water and air dried. White solid,
0.920 g ( 91 %), m.p. 133–136
0
C. Anal. Calc. for
C26H20BrOP: C: 67.99; H: 4.39; Found: C: 68.15; H:
4.42. IR (KBr disk): ν 1520.82 (CO) and 876.50 (P
+
-C
-
)
cm
–1
.
1
HNMR (CDCl3) δ= 4.39 (d,
2
JPH =23.38 Hz,
1H, CH) and 7.27-8.09 ppm (m, 19H, arom.).
31
P NMR
(CDCl3) δ :13.22 ppm (s).
13
C NMR (CDCl3) δ : 53.25
ppm (s,1C , CH), 125.13-135.41 ppm (m, C6H5), and
195.25 ppm (s, CO).
2.2.3. Synthesis of Hg(II) halide complexes (1-3)
General procedure. To a methanolic solution (15 ml)
of HgX2 (1 mmol) was added a methanolic solution (10
ml) of L (0.459 g, 1 mmol). The mixture was stirred for
4 h. The separated solid was filtered and washed with
diethyl ether.
Data for [L.HgCl2]2 (1): white solid, 86 %, m.p. 160–
163
0
C. Anal. Calc. for C52H40Br2O2P2Hg2Cl2: C: 44.91;
H: 2.90. Found: C: 45.13; H: 2.94. IR (KBr disk) ν:
1625.88(CO) and 829.79 (P
+
-C
-
) cm
–1
.
1
HNMR
(CDCl3) δ: 5.27 (s, 1H, CH) and 7.26-8.11 ppm (m,
19H, arom.).
31
P NMR (CDCl3) δ: 22.60 ppm (s).
13
C
NMR (CDCl3) δ : 28.40 ppm (s, 1C, CH), 122.43-
136.47 ppm (m, 24C,arom), and 187.89 ppm (s, CO).
Data for [L.HgBr2]2 (2): white solid, Salt: 95 %, m.p.
153–157
0
C. Anal. Calc. for C52H40Br6O2P2Hg2: C:
38.10; H: 2.46. Found: C: 39.05; H: 2.49. IR (KBr disk)
ν: 1624.14 (CO) and 824.87 (P
+
-C
-
) cm
–1
.
1
HNMR
(CDCl3) δ: 5.72 (s, 1H, CH) and 7.27-8.15 ppm (m,
19H, arom.).
31
P NMR (CDCl3) δ: 22.32 ppm(s).
13
C
NMR (CDCl3) δ : 29.4 ppm (s, CH), 122.43-136.45
ppm (m, 24C, arom), and 188.86 ppm (s, CO).
Data for [L.HgI2]2 (3): yellow solid, Salt: 54 %, m.p.
170–174
0
C. Anal. Calc. for C52H40Br2O2P2Hg2I4: C:
34.18; H: 2.21. Found: C: 34.82; H: 2.27. IR (KBr disk)
ν: 1634.50 (CO) and 824.39 (P
+
-C
-
) cm
–1
.
1
HNMR
(CDCl3) δ: 5.59 (s, 1H, CH) and 7.26-8.14 ppm (m,
19H, arom.).
31
P NMR (CDCl3) δ: 18.32 ppm(s).
13
C
NMR (CDCl3) δ : 24.6 ppm (s, 1C , CH), 127.09-
136.49 ppm (m, 24C,arom), and 187.01 ppm (s, CO).
Int. J. Curr.Res.Chem.Pharma.Sci. 2(8): (2015):7–16
© 2015, IJCRCPS. All Rights Reserved 9
2.2.4. Synthesis of Cd(II) nitrate complexe (4)
A solution (1 mmol) of Cd(NO3)2.4H2O (0.312 g, 1
mmol) in dry methanol (5 mL) was added to a solution
(0.459 g , 1 mmol) of L in dry methanol and stirred for
30 min at room temperature. The white solution was
concentrated to 2mL and diethyl ether (15 mL) was
added to precipitate the dinuclear complex which was
recrystallized from chloroform–diethyl ether and dried
in vacuum. White solid, 0.695 g (85%), m.p. 160.3 –
162.7
0
C. Anal. Calc. for C26H20BrPN2O7Cd: C: 44.88;
H: 2.90; N: 4.03. Found: C: 45.23; H: 2.96; N: 3.92. IR
(KBr disk) ν: 1681.93 (CO) and 825.35 (P
+
-C
-
) cm
–1
.
1
HNMR (CDCl3) δ: 5.67 (d,
2
JPH =12.45 Hz, 1H, CH)
and 7.26 - 8.22 ppm (m, 19H, arom.).
31
P NMR
(CDCl3) δ: 17.48 ppm (s).
2.2.5. Synthesis of the Ag(I) complexes (5 and 6)
General procedure. To AgNO3 (0.169 g, 1 mmol)
and AgOTF (0.256 g, 1mmol) dissolved in 5 mL of
dried methanol was added the L (0.450 g, 1 mmol).
The mixture was stirred for 4 h, during which time it
was protected from light. The white solid product was
filtered, washed with Et2O and dried under reduced
pressure.
Data for [Ag.(L)2]NO3 (5). white solid, 0581 g (92 %),
m.p. 170.2 – 174.5
0
C. Anal. Calc. for
C52H40Br2P2NO5Ag: C: 57.38; H: 3.70; N: 1.29. Found:
C: 57.89; H: 3.81; N: 1.21. IR (KBr disk) ν: 1678.14
(CO) and 856.26 (P
+
-C
-
) cm
–1
.
1
HNMR (CDCl3) δ: 5.98
(d,
2
JPH =12.18 Hz , 1H, CH) and 7.49 – 8.11 ppm (m,
19H, arom.).
31
P NMR (CDCl3) δ: 22.97 ppm (s).
13
C
NMR (CDCl3) δ: 29.12 ppm (s, 1C, CH), 127.87- 136.6
ppm (m, 24C, arom.), and 187.96 ppm (s, CO).
Data for [Ag.(L)2]OTF (6). white solid, 0.642 g (89%),
m.p. 109.2 -112.7
0
C. Anal. Calc. for
CF3SO5C52H40Br2P2Ag: C: 54.15; H: 3.43. Found: C:
54.67; H: 3.55. IR (KBr disk) ν: 1683.94 (CO) and
845.63 (P
+
-C
-
) cm
–1
.
1
HNMR (CDCl3) δ: 5.62 (d,
2
JPH
=13.08 Hz, 1H, CH) and 7.25-8.28 ppm (m, 19H,
arom.).
31
P NMR (CDCl3) δ: 22.85 ppm (s).
13
C NMR
(CDCl3) δ : 24.6 ppm (s, 1C , CH), 127.09-136.33 ppm
(m, 24C, arom.), and 187.02 ppm (s, CO).
2.3. Antibacterial activity
The potential antibacterial effects of the metal
complexes were investigated against three Gram
positive bacteria, namely Bacillus cereus (PTCC
1247), Staphylococcus aureus (Wild) and Bacillus
megaterium (PTCC 1017), and three Gram negative
bacteria, namely Escherichia coli (Wild), Proteus
vulgaris (PTCC 1079), and Serratiamarcescens
(PTCC 1111) by disc diffusion method (Awoyinka et
al., 2007). The complexes were dissolved in DMSO to
a final concentration of 1 mg ml
-1
and then sterilized by
filtration using 0.45 μm millipore. All tests were carried
using 10 ml of suspension containing 1.5 × 10
8
bacteria/ml and spread on nutrient agar medium.
Negative controls were prepared by using DMSO.
Gentamycin, penicillin and neomycin were used as
positive reference standards. The diameter of
inhibition zones generated by the complexes was
measured.
Results and Discussion
3.1. Synthesis
The ligand (L) was synthesized by treating 2, 3′-
dibromoacetophenone with triphenylphosphine and
removal of the proton from the phosphonium salt (See
Scheme 2).
Scheme 2. The synthesis route for preparation of phosphonium salt (S) and related ylide (L)
Int. J. Curr.Res.Chem.Pharma.Sci. 2(8): (2015):7–16
© 2015, IJCRCPS. All Rights Reserved 10
Reaction of the ligand with HgX2 (X = Cl, Br and I)
(1:1) yielded the binuclear complexes (see Scheme 3).
CH
CO
CH
O
Hg
X
X
Hg
X
C
X
Br
Br
Br
C C H PPh3
O
+ H gX 2
X=C l , Br , I
PPh3
PPh3
Scheme 3. Synthetic route for preparation of Hg(II) complexes
The compounds derived from phosphorus ylide with
Cd(NO3)2.4H2O form polynuclear structures with
nitrate anions in the bridges (Scheme 4).
Cd
O
O
N
O
CH
OO
N
O
P C
O
n
Br
+ Cd(NO3)2.4H2O
Br
C CH PPh3
O
Scheme 4. Synthetic route for preparation of Cd(II) complex
The reaction of ylide with AgX (X = NO3, OTF) in a 2:1
molar ratio in dichloromethane as solvent gave
mononuclear complexes (see Scheme 5).
Br
C CH PPh3
O
Ag CH
P
CO
CH
P
C O
X
Br
Br
+ AgX
X = NO3 , OTF
Scheme 5. Synthetic route for preparation of Ag complexes
Int. J. Curr.Res.Chem.Pharma.Sci. 2(8): (2015):7–16
© 2015, IJCRCPS. All Rights Reserved 11
3.2. Spectroscopy
The shift to higher energy of ν(CO) in complexes
relative to the free ylide (Table 1) suggests
coordination of the ylide through the carbon atom.
Coordination through the carbon atom causes an
increase in ν(CO), while O-coordination gives a
lowering of ν(CO). The infrared spectra of complexes
in the solid state show ν(CO) from 1624–1681 cm
-1
,
which is at higher frequencies with respect to the free
ylide. The ν(P
+
–C
-
) frequency, which is also diagnostic
of coordination, occurs at 876 cm
-1
for the ylide. In the
present study the ν(P
+
–C
-
) values for all the
complexes were shifted to lower frequencies; i.e.,
observed from 824–859 cm
-1
. This suggests some
removal of electron density from the P–C bond (Onishi
et al., 1982; Sabounchei et al., 2007). In the
1
H NMR
spectra, methinic protons exhibit a broad or broad
doublet signals. Similar behavior was observed earlier
in the case of ylide complexes of platinum(II) chloride
(Teagle and Burmeister, 1986). The
31
P{
1
H} NMR
spectra of these complexes show only one sharp
singlet between 17.48 ppm and 22.97 ppm. The
31
P
chemical shift values for the complexes appear at
higher frequency by about 4–10 ppm relative to the
parent ylides ( = 13.22 ppm for L), which indicates
that coordination of the ylide occurred (Table 1). The
appearance of one set of signals for the PCH group in
both the
31
P and
1
H NMR spectra indicates the
presence of only one molecule for all complexes
(Kalyanasundari et al., 1995). The most interesting
aspect of the
13
C NMR spectra of the complexes is the
upfield shift of the signals due to the ylidic carbon
atoms. Such an upfield shift is due to the change in
hybridization of the ylidic carbon atom on coordination.
Similar up field shifts of 2–3 ppm with reference to the
parent ylide were also observed in the case of
[(C6H5)3PC5H4HgI2]2 (Holy et al., 1976). The downfield
shifts of the carbonyl C atom in the complexes
compared to the same carbon atom in the parent ylide,
indicate a much lower shielding of the CO group in
these complexes.
Table 1. Selected
1
H and
31
P NMR [δ (ppm), J (Hz)] and IR(cm
-1
) data for the salt (S), ligand (L) and corresponding
complexes (1-6)
Compound C(CO) δ CH2 δ PCH2 δ CH (
2
JP–H) ʋ(CO) ʋ(PC)
S 190.56 37.75(d) 18.39(s) 6.34(d) 1676 859.37
L 195.25 53.25(br) 13.22(s) 4.39(d) 1520 876.50
HgCl2 (1) 187.89 28.40(br) 22.60(s) 5.27(br) 1625 829.79
HgBr2 (2) 188.86 29.4(br) 22.32(s) 5.72(br) 1624 824.87
HgI2 (3) 187.01 24.6(br) 18.32(s) 5.59(br) 1634 824.39
Cd(NO3)2 (4) - - 17.48(s) 5.67(d) 1681 825.35
AgNO3 (5) 187.96 29.12(br) 22.97(s) 5.98(d) 1678 856.26
AgOTF (6) 187.02 24.6(br) 22.85(s) 5.62(d) 1683 845.63
S (singlet), br ( broad), d (doublet)
Figure S1.
31
P NMR Spectrum of compound S
Int. J. Curr.Res.Chem.Pharma.Sci. 2(8): (2015):7–16
© 2015, IJCRCPS. All Rights Reserved 12
Figure S2.
1
H NMR Spectrum of compound S
Figure S3.
13
C NMR Spectrum of compound S
Figure S4.
31
P NMR Spectrum of compound L
Int. J. Curr.Res.Chem.Pharma.Sci. 2(8): (2015):7–16
© 2015, IJCRCPS. All Rights Reserved 13
Figure S5.
1
H NMR Spectrum of compound L
Figure S6.
31
P NMR Spectrum of compound 3
Figure S7.
1
H NMR Spectrum of compound 3
Int. J. Curr.Res.Chem.Pharma.Sci. 2(8): (2015):7–16
© 2015, IJCRCPS. All Rights Reserved 14
3.3. Antibacterial activity
Our results demonstrated that all studied complexes
display antibacterial activity against the bacteria tested
especially Gram positive ones. With comparing
antibacterial activity of the complexes with those of
reference antibiotics, it seems that they have
remarkable inhibitory potency against bacteria.Results
from antibacterial assessment of the samples and
from positive and negative controls are in Tables 2
and 3. The test compounds were dissolved in DMSO
at concentrations of 1, 0.1 and 0.01 mgml
-1
. DMSO
which was used as a solvent was also screened
against all bacteria. It has no activity against the
bacteria. Generally the antibacterial activity of
compounds is attributed mainly to its major
components. However, today it is known that the
synergistic or antagonistic effect of one compound,
even when it is a minor component of mixture has to
be considered (Burt, 2004). The complexes reported
here showed more activity against some bacteria, than
othersat the same identical experimental conditions.
This would suggest that the structure of complexes
may reduce the polarity of the metal ion mainly.
Perhaps a neutral coordination complex may also
transport easily from the lipid phase of the bacterial
cell membrane and then affected growth and
development (Fahmi et al., 1998; Tumer et al., 2007).
Composition of the coordination site and the geometry
of the tested complexes seemed to be the principal
factors that influence antibacterial activity. However,
the complexes studied here may be used in treatment
of the diseases caused by tested bacteria.
Table 2. Antibacterial activity ligand (L) and corresponding complexes (1-6).
Compound Concentratio
n
Inhibition zone (mm)
P. v (-) E. c (-) B. c (+) S. a (+) B. m(+) S. m (-)
L
1 (mg/ml) 15 ± 0.32
a
10 ± 0.28
a
7 ± 0.00 10 ± 0.11
a
11 ± 0.13
a
14 ± 0.54
a
0.1(mg/ml) 12 ± 0.14
b
9 ± 0.35
b
Na 7 ± 0.18
b
8 ± 0.28
b
11 ± 0.22
b
0.01(mg/ml) 7 ± 0.00
c
7 ± 0.00
c
Na Na 8 ± 0.54
b
8 ± 0.18
c
1 1(mg/ml) 16± 0.33
a
18 ± 0.16
a
20 ± 0.14
a
21 ± 0.14
a
25 ± 0.12
a
10 ± 0.66
a
0.1(mg/ml) 12 ± 0.35
b
11 ± 0.15
b
17 ± 0.33
b
16 ± 0.34
b
15 ± 0.25
b
8 ± 0.27
b
0.01(mg/ml) 8 ± 0.24c 7 ± 0.00
c
10 ± 0.18
c
10 ± 0.26
c
11 ± 0.35c Na
2 1(mg/ml) 16 ± 0.43
a 30 ± 0.25
a
19 ± 0.26
a
17 ± 0.25
a
16 ± 0.14a 11 ± 0.46
a
0.01(mg/ml) 11 ± 0.24
b
22 ± 0.23
b
13 ± 0.20
b
13 ± 0.25
b
12 ± 0.18
b
8 ± 0.11
b
0.01(mg/ml) 8 ± 0.10
c
14 ± 0.18
c
Na Na Na Na
3 1(mg/ml) 16 ± 0.26
a
15 ± 0.26
a
21 ± 0.38
a
17 ± 0.24
a
14 ± 0.10
a
14 ± 0.26
a
0.1(mg/ml) 11 ± 0.18
b
10 ± 0.18
b
14 ± 0.15
b
14 ± 0.00
b
11 ± 0.15
b
8 ± 0.27
b
0.01(mg/ml) 8 ± 0.24
c
7 ± 0.24
c
10 ± 0.24
c
11 ± 0.34
c 8 ± 0.18
c
7 ± 0.00
c
1(mg/ml) 14 ± 0.13
a
13 ± 0.14
a
11 ± 0.16
a
16± 0.13
a
12 ± 0.16
a
14 ± 0.34
a
4 0.1(mg/ml) 11 ± 0.24
b
9 ± 0.21
b
8 ± 0.15
b
11 ± 0.33
b
8 ± 0.23
b
10 ± 0.21
b
0.01(mg/ml) 8 ± 0.15
c
9 ± 0.18
b
7 ± 0.11
c
10 ± 0.11
c
8 ± 0.15
b
8 ± 0.00
c
1(mg/ml) 14 ± 0.16
a
15 ± 0.33
a
13 ± 0.16
a
18 ± 0.25
a
11 ± 0.14
a
14 ± 0.33
a
5 0.1(mg/ml) 10 ± 0.24
b
14 ± 0.15
b
10 ± 0.45
b
13 ± 0.10
b
8 ± 0.26
b
10 ± 0.11
b
0.01(mg/ml) 8 ± 0.21
c
10 ± 0.00
c
8 ± 0.14
c
8 ± 0.14
c
Na 8 ± 0.15
c
1(mg/ml) 16 ± 0.12
a
14 ± 0.38
a
14 ± 0.17
a
17 ± 0.34
a 12 ± 0.23
a
13 ± 0.18
a
6 0.1(mg/ml) 12 ± 0.14
b
11 ± 0.35
b
9 ± 0.15
b
15 ± 0.11
b
8 ± 0.16
b
9 ± 0.73
b
0.01(mg/ml) 10 ± 0.45
c
10 ± 0.25
c
8 ± 0.13
c
10 ± 0.11
c 7 ± 0.27
c
7 ± 0.25
c
Experiment was performed in triplicate and expressed as mean ± SD. Values with different superscripts within each
column (for any bacteria in different concentrations) are significantly different (P < 0.05).
Na: no active.
Int. J. Curr.Res.Chem.Pharma.Sci. 2(8): (2015):7–16
© 2015, IJCRCPS. All Rights Reserved 15
Table 3. Antibacterial activity of antibiotics as positive controls and DMSO as negative control.
Experiment was performed in triplicate and expressed as mean ± SD. Values with different superscripts within
each column (for any bacteria in different concentrations) aresignificantly different (P < 0.05).
Na: no active
Conclusions
The present study describes the synthesis and
characterization of a new series of Hg(II), Cd(II) and
Ag(I) complexes of a monodentate phosphorus ylide.
On the basis of the physical–chemical and
spectroscopic data we propose that the ligands
described herein exhibit monodentate C-coordination
to the metal center. In addition, the metal complexes
represent significant antibacterial activity, which may
help us to design of improved antibacterial agents.
Acknowledgments
We are grateful to Bu-Ali Sina University for financial
support.
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Microorganism Inhibition zone (mm)
Gentamicin Penicilli
n
Nitrofurantion Neomyci
n
DMSO
Proteus vulgaris (−) 28 ± 0.64 NA 18 ± 0.23 21 ± 0.45 NA
Escherichia coli (−) NA NA 23 ± 0.33 24 ± 0.16 NA
Bacillus cereus (+) 22 ± 0.57 NA 12 ± 0.28 18 ± 0.17 NA
Staphylococcus
aureus(+)
37 ± 0.21 NA 30 ± 0.22 24 ± 0.28 NA
Bacillus megaterium(+) 25 ± 0.44 NA 23 ± 0.46 18 ± 0.26 NA
Serratiamarcescens(−) 22 ± 0. 22 NA 18 ± 0.44 25 ± 0.33 NA
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SYNTHESIS AND CHARACTERIZATION OF SOME TRANSITION METAL COMPLEXES WITH A NEW MONODENTATE PHOSPHORUS YIELD AND THEIR ANTIBACTERIAL ACTIVITIES

  • 1. Int. J. Curr.Res.Chem.Pharma.Sci. 2(8): (2015):7–16 © 2015, IJCRCPS. All Rights Reserved 7 INTERNATIONAL JOURNAL OF CURRENT RESEARCH IN CHEMISTRY AND PHARMACEUTICAL SCIENCES (p-ISSN: 2348-5213: e-ISSN: 2348-5221) www.ijcrcps.com Research Article SYNTHESIS AND CHARACTERIZATION OF SOME TRANSITION METAL COMPLEXES WITH A NEW MONODENTATE PHOSPHORUS YIELD AND THEIR ANTIBACTERIAL ACTIVITIES SEYYED JAVAD SABOUNCHEIA,* , SOMAYEH NAZARYANI FARDA , MAHBUBEH POURSHAHBAZA , ROYA KARAMIANB , MOSTAFA ASADBEGYB A Faculty of Chemistry, Bu-Ali sina University, Hamedan, 65174, Iran B Department of Biology, Faculty of Science, Bu-Ali Sina University, Hamedan 65174, Iran *Corresponding Author Abstract A new monodentate phosphorus yield Ph3P=CHC(O)C6H4-m-Br (L),was synthesized and characterized with elemental analysis as well as various spectroscopic techniques. The reactions of the title ylide with mercury(II) halides in equimolar ratios using dry methanol as solvent have yielded [L.HgX2]2 (X= Cl (1), Br (2), I (3)). The reaction of 1 equiv. this ylide with Cd(NO3)2.4H2O in the same solvent give a polynuclear complex [Cd (L)(NO3)(μ-NO3)]n (4), followed by treatment with 2 equiv. AgNO3 and AgOTf led to monomeric chelate complexes 5 and 6, respectively. Characterization of the obtained compounds was also performed by elemental analysis, IR, 1 H, 31 P and 13 C NMR. All DMSO-solved synthesized compounds were subjected to biological evaluation for their antibacterial against 6 Gram positive and negative bacteria effects by disc diffusion method. Results showed antibacterial activity for studied metal complexes and suggested their possible application as antibacterial agents. Keywords: Phosphorus yields, mercury(II) complexes, silver(I) complexes, cadmium(II) complexes, antibacterial activity. Introduction The utility of metalated phosphorus ylides in synthetic chemistry has been well documented (Christau, 1994; Kolodiazhnyi, 1996). The keto group in the a-keto stabilized phosphorus ylides cause resonance delocalization and provide additional stabilization to the ylide species (Scheme 1). The synthesis of complexes derived from ylides and Ag(I) began in 1975 by Yamamoto et al. (Yamamoto and Schmidbaur, 1975). Other types of ylide complexes of silver(I) have been reported (Schmidbaur et al., 1973; Schmidbaur et al., 1974; Schmidbaur and Richer, 1975; Yamamoto and Schmidbaur, 1975; Schmidbaur and Scherm, 1977;). In 1987 and 1983, Vicente et al. (Vicente et al., 1987; Vicente et al., 1993) reported the crystal structures of Ag(I) complexes of phosphorus ylides. The synthesis of complexes derived from phosphorus ylides and Hg(II) salts was limited to Hg(II) halides and was started in 1965 by Nesmeyanov et al. (Nesmeyanov et al., 1965). Weleski et al. (Weleski et al., 1975) in 1975 proposed a symmetric halide-bridged dimeric structure for Hg(II) halide complexes, while Kalyanasundari et al. (Kalyanasundari et al., 1995) in 1995 reported an asymmetric halide bridged structure. Antimicrobial resistance is fast becoming a global concern with rapid promotion in multidrug resistant bacteria (Bennett, 2008). Development of metal complexes are able to inhibit bacterial growth has been of great interest in recent years due to their potential use in paints, kitchenware, school and hospital utensils, etc. Metal complexes play important roles in many biological systems (Kamalakannan, and Venkappayya, 2002; Islam et al., 2002; Agwara et al., 2011). This revival interest was generated by the discovery of antibacterial activity of several metal complexes (Saha et al., 2009; Sabounchei et al., 2013). Although some Hg(II) complexes are among the most widely used antibacterial agents, it seem that the assessment of antibacterial activity of new metal complexes with ligands system is
  • 2. Int. J. Curr.Res.Chem.Pharma.Sci. 2(8): (2015):7–16 © 2015, IJCRCPS. All Rights Reserved 8 very necessary. In this study, we describe the preparation, spectroscopic characterization and antibacterial activities of Hg(II), Cd(II) and Ag(I)complexes with the title ylide. Scheme 1. Resonance forms for a ketostabilized phosphorus ylide Materials and Methods 2.1. Chemicals and Instrumentation All reactions were performed in air. All other chemicals were reagent grade and were used without further purification. Elemental analysis for C, H and N were performed using a Perkin-Elmer 2400 series analyzer. IR spectra were recorded on a Shimadzu 435-U-04 spectrophotometer in a region 4000-550 cm -1 and the measurements were made by the KBr disk method. Melting points were measured on a SMP3 apparatus. Solution-state 1 H, 31 P and 13 C NMR spectra were recorded on 400 MHz Bruker and 90 MHz Jeol spectrometer in CDCl3 as solvent at 25 ºC. Chemical shifts (ppm) are reported according to internal TMS and external 85% phosphoric acid. 2.2. Synthesis and Characterization 2.2.1. Synthesis of monophosphonium salt [Ph3PCH2C(O)C6H4-m-Br]Br (S) Triphenylphosphine (0.262 g, 1 mmol) was dissolved in 5 ml of acetone and then a solution of 2,3-di bromoacetophenone (0.277 g, 1 mmol) in the same solvent (5 ml) was added dropwise to the above solution. The resulting yellow solution was stirred for 4 h. The solution was concentrated under reduced pressure to 2 ml, and diethyl ether (20 ml) was added. The white solid formed was filtered off, washed with diethyl ether (210 ml) and dried under reduced pressure. White solid, 0.269 g (50 %), m.p. 82–85 0 C. Anal. Calc. for C26H21Br2OP: C: 57.81; H: 3.92; Found: C: 57.98; H: 3.96.; IR (KBr disk) ν: 1676.34(CO) and 859.37 (P + -C - ) cm –1 . 1 HNMR (CDCl3) δ: 6.34 (d, 2 JPH =12.18 Hz, 2H, CH2) and 7.26 – 8.58 ppm (m, 19H, arom.). 2.2.2. Synthesis of monodentate phosphorus ylide [Ph3P=CHC(O)C6H4-m-Br] (L) The phosphonium salt (S) (0.533 gr, 1 mmol) was transferred to an aqueous NaOH (5 %) and stirred at 40°C for 24 h. The white product was obtained, washed with distilled water and air dried. White solid, 0.920 g ( 91 %), m.p. 133–136 0 C. Anal. Calc. for C26H20BrOP: C: 67.99; H: 4.39; Found: C: 68.15; H: 4.42. IR (KBr disk): ν 1520.82 (CO) and 876.50 (P + -C - ) cm –1 . 1 HNMR (CDCl3) δ= 4.39 (d, 2 JPH =23.38 Hz, 1H, CH) and 7.27-8.09 ppm (m, 19H, arom.). 31 P NMR (CDCl3) δ :13.22 ppm (s). 13 C NMR (CDCl3) δ : 53.25 ppm (s,1C , CH), 125.13-135.41 ppm (m, C6H5), and 195.25 ppm (s, CO). 2.2.3. Synthesis of Hg(II) halide complexes (1-3) General procedure. To a methanolic solution (15 ml) of HgX2 (1 mmol) was added a methanolic solution (10 ml) of L (0.459 g, 1 mmol). The mixture was stirred for 4 h. The separated solid was filtered and washed with diethyl ether. Data for [L.HgCl2]2 (1): white solid, 86 %, m.p. 160– 163 0 C. Anal. Calc. for C52H40Br2O2P2Hg2Cl2: C: 44.91; H: 2.90. Found: C: 45.13; H: 2.94. IR (KBr disk) ν: 1625.88(CO) and 829.79 (P + -C - ) cm –1 . 1 HNMR (CDCl3) δ: 5.27 (s, 1H, CH) and 7.26-8.11 ppm (m, 19H, arom.). 31 P NMR (CDCl3) δ: 22.60 ppm (s). 13 C NMR (CDCl3) δ : 28.40 ppm (s, 1C, CH), 122.43- 136.47 ppm (m, 24C,arom), and 187.89 ppm (s, CO). Data for [L.HgBr2]2 (2): white solid, Salt: 95 %, m.p. 153–157 0 C. Anal. Calc. for C52H40Br6O2P2Hg2: C: 38.10; H: 2.46. Found: C: 39.05; H: 2.49. IR (KBr disk) ν: 1624.14 (CO) and 824.87 (P + -C - ) cm –1 . 1 HNMR (CDCl3) δ: 5.72 (s, 1H, CH) and 7.27-8.15 ppm (m, 19H, arom.). 31 P NMR (CDCl3) δ: 22.32 ppm(s). 13 C NMR (CDCl3) δ : 29.4 ppm (s, CH), 122.43-136.45 ppm (m, 24C, arom), and 188.86 ppm (s, CO). Data for [L.HgI2]2 (3): yellow solid, Salt: 54 %, m.p. 170–174 0 C. Anal. Calc. for C52H40Br2O2P2Hg2I4: C: 34.18; H: 2.21. Found: C: 34.82; H: 2.27. IR (KBr disk) ν: 1634.50 (CO) and 824.39 (P + -C - ) cm –1 . 1 HNMR (CDCl3) δ: 5.59 (s, 1H, CH) and 7.26-8.14 ppm (m, 19H, arom.). 31 P NMR (CDCl3) δ: 18.32 ppm(s). 13 C NMR (CDCl3) δ : 24.6 ppm (s, 1C , CH), 127.09- 136.49 ppm (m, 24C,arom), and 187.01 ppm (s, CO).
  • 3. Int. J. Curr.Res.Chem.Pharma.Sci. 2(8): (2015):7–16 © 2015, IJCRCPS. All Rights Reserved 9 2.2.4. Synthesis of Cd(II) nitrate complexe (4) A solution (1 mmol) of Cd(NO3)2.4H2O (0.312 g, 1 mmol) in dry methanol (5 mL) was added to a solution (0.459 g , 1 mmol) of L in dry methanol and stirred for 30 min at room temperature. The white solution was concentrated to 2mL and diethyl ether (15 mL) was added to precipitate the dinuclear complex which was recrystallized from chloroform–diethyl ether and dried in vacuum. White solid, 0.695 g (85%), m.p. 160.3 – 162.7 0 C. Anal. Calc. for C26H20BrPN2O7Cd: C: 44.88; H: 2.90; N: 4.03. Found: C: 45.23; H: 2.96; N: 3.92. IR (KBr disk) ν: 1681.93 (CO) and 825.35 (P + -C - ) cm –1 . 1 HNMR (CDCl3) δ: 5.67 (d, 2 JPH =12.45 Hz, 1H, CH) and 7.26 - 8.22 ppm (m, 19H, arom.). 31 P NMR (CDCl3) δ: 17.48 ppm (s). 2.2.5. Synthesis of the Ag(I) complexes (5 and 6) General procedure. To AgNO3 (0.169 g, 1 mmol) and AgOTF (0.256 g, 1mmol) dissolved in 5 mL of dried methanol was added the L (0.450 g, 1 mmol). The mixture was stirred for 4 h, during which time it was protected from light. The white solid product was filtered, washed with Et2O and dried under reduced pressure. Data for [Ag.(L)2]NO3 (5). white solid, 0581 g (92 %), m.p. 170.2 – 174.5 0 C. Anal. Calc. for C52H40Br2P2NO5Ag: C: 57.38; H: 3.70; N: 1.29. Found: C: 57.89; H: 3.81; N: 1.21. IR (KBr disk) ν: 1678.14 (CO) and 856.26 (P + -C - ) cm –1 . 1 HNMR (CDCl3) δ: 5.98 (d, 2 JPH =12.18 Hz , 1H, CH) and 7.49 – 8.11 ppm (m, 19H, arom.). 31 P NMR (CDCl3) δ: 22.97 ppm (s). 13 C NMR (CDCl3) δ: 29.12 ppm (s, 1C, CH), 127.87- 136.6 ppm (m, 24C, arom.), and 187.96 ppm (s, CO). Data for [Ag.(L)2]OTF (6). white solid, 0.642 g (89%), m.p. 109.2 -112.7 0 C. Anal. Calc. for CF3SO5C52H40Br2P2Ag: C: 54.15; H: 3.43. Found: C: 54.67; H: 3.55. IR (KBr disk) ν: 1683.94 (CO) and 845.63 (P + -C - ) cm –1 . 1 HNMR (CDCl3) δ: 5.62 (d, 2 JPH =13.08 Hz, 1H, CH) and 7.25-8.28 ppm (m, 19H, arom.). 31 P NMR (CDCl3) δ: 22.85 ppm (s). 13 C NMR (CDCl3) δ : 24.6 ppm (s, 1C , CH), 127.09-136.33 ppm (m, 24C, arom.), and 187.02 ppm (s, CO). 2.3. Antibacterial activity The potential antibacterial effects of the metal complexes were investigated against three Gram positive bacteria, namely Bacillus cereus (PTCC 1247), Staphylococcus aureus (Wild) and Bacillus megaterium (PTCC 1017), and three Gram negative bacteria, namely Escherichia coli (Wild), Proteus vulgaris (PTCC 1079), and Serratiamarcescens (PTCC 1111) by disc diffusion method (Awoyinka et al., 2007). The complexes were dissolved in DMSO to a final concentration of 1 mg ml -1 and then sterilized by filtration using 0.45 μm millipore. All tests were carried using 10 ml of suspension containing 1.5 × 10 8 bacteria/ml and spread on nutrient agar medium. Negative controls were prepared by using DMSO. Gentamycin, penicillin and neomycin were used as positive reference standards. The diameter of inhibition zones generated by the complexes was measured. Results and Discussion 3.1. Synthesis The ligand (L) was synthesized by treating 2, 3′- dibromoacetophenone with triphenylphosphine and removal of the proton from the phosphonium salt (See Scheme 2). Scheme 2. The synthesis route for preparation of phosphonium salt (S) and related ylide (L)
  • 4. Int. J. Curr.Res.Chem.Pharma.Sci. 2(8): (2015):7–16 © 2015, IJCRCPS. All Rights Reserved 10 Reaction of the ligand with HgX2 (X = Cl, Br and I) (1:1) yielded the binuclear complexes (see Scheme 3). CH CO CH O Hg X X Hg X C X Br Br Br C C H PPh3 O + H gX 2 X=C l , Br , I PPh3 PPh3 Scheme 3. Synthetic route for preparation of Hg(II) complexes The compounds derived from phosphorus ylide with Cd(NO3)2.4H2O form polynuclear structures with nitrate anions in the bridges (Scheme 4). Cd O O N O CH OO N O P C O n Br + Cd(NO3)2.4H2O Br C CH PPh3 O Scheme 4. Synthetic route for preparation of Cd(II) complex The reaction of ylide with AgX (X = NO3, OTF) in a 2:1 molar ratio in dichloromethane as solvent gave mononuclear complexes (see Scheme 5). Br C CH PPh3 O Ag CH P CO CH P C O X Br Br + AgX X = NO3 , OTF Scheme 5. Synthetic route for preparation of Ag complexes
  • 5. Int. J. Curr.Res.Chem.Pharma.Sci. 2(8): (2015):7–16 © 2015, IJCRCPS. All Rights Reserved 11 3.2. Spectroscopy The shift to higher energy of ν(CO) in complexes relative to the free ylide (Table 1) suggests coordination of the ylide through the carbon atom. Coordination through the carbon atom causes an increase in ν(CO), while O-coordination gives a lowering of ν(CO). The infrared spectra of complexes in the solid state show ν(CO) from 1624–1681 cm -1 , which is at higher frequencies with respect to the free ylide. The ν(P + –C - ) frequency, which is also diagnostic of coordination, occurs at 876 cm -1 for the ylide. In the present study the ν(P + –C - ) values for all the complexes were shifted to lower frequencies; i.e., observed from 824–859 cm -1 . This suggests some removal of electron density from the P–C bond (Onishi et al., 1982; Sabounchei et al., 2007). In the 1 H NMR spectra, methinic protons exhibit a broad or broad doublet signals. Similar behavior was observed earlier in the case of ylide complexes of platinum(II) chloride (Teagle and Burmeister, 1986). The 31 P{ 1 H} NMR spectra of these complexes show only one sharp singlet between 17.48 ppm and 22.97 ppm. The 31 P chemical shift values for the complexes appear at higher frequency by about 4–10 ppm relative to the parent ylides ( = 13.22 ppm for L), which indicates that coordination of the ylide occurred (Table 1). The appearance of one set of signals for the PCH group in both the 31 P and 1 H NMR spectra indicates the presence of only one molecule for all complexes (Kalyanasundari et al., 1995). The most interesting aspect of the 13 C NMR spectra of the complexes is the upfield shift of the signals due to the ylidic carbon atoms. Such an upfield shift is due to the change in hybridization of the ylidic carbon atom on coordination. Similar up field shifts of 2–3 ppm with reference to the parent ylide were also observed in the case of [(C6H5)3PC5H4HgI2]2 (Holy et al., 1976). The downfield shifts of the carbonyl C atom in the complexes compared to the same carbon atom in the parent ylide, indicate a much lower shielding of the CO group in these complexes. Table 1. Selected 1 H and 31 P NMR [δ (ppm), J (Hz)] and IR(cm -1 ) data for the salt (S), ligand (L) and corresponding complexes (1-6) Compound C(CO) δ CH2 δ PCH2 δ CH ( 2 JP–H) ʋ(CO) ʋ(PC) S 190.56 37.75(d) 18.39(s) 6.34(d) 1676 859.37 L 195.25 53.25(br) 13.22(s) 4.39(d) 1520 876.50 HgCl2 (1) 187.89 28.40(br) 22.60(s) 5.27(br) 1625 829.79 HgBr2 (2) 188.86 29.4(br) 22.32(s) 5.72(br) 1624 824.87 HgI2 (3) 187.01 24.6(br) 18.32(s) 5.59(br) 1634 824.39 Cd(NO3)2 (4) - - 17.48(s) 5.67(d) 1681 825.35 AgNO3 (5) 187.96 29.12(br) 22.97(s) 5.98(d) 1678 856.26 AgOTF (6) 187.02 24.6(br) 22.85(s) 5.62(d) 1683 845.63 S (singlet), br ( broad), d (doublet) Figure S1. 31 P NMR Spectrum of compound S
  • 6. Int. J. Curr.Res.Chem.Pharma.Sci. 2(8): (2015):7–16 © 2015, IJCRCPS. All Rights Reserved 12 Figure S2. 1 H NMR Spectrum of compound S Figure S3. 13 C NMR Spectrum of compound S Figure S4. 31 P NMR Spectrum of compound L
  • 7. Int. J. Curr.Res.Chem.Pharma.Sci. 2(8): (2015):7–16 © 2015, IJCRCPS. All Rights Reserved 13 Figure S5. 1 H NMR Spectrum of compound L Figure S6. 31 P NMR Spectrum of compound 3 Figure S7. 1 H NMR Spectrum of compound 3
  • 8. Int. J. Curr.Res.Chem.Pharma.Sci. 2(8): (2015):7–16 © 2015, IJCRCPS. All Rights Reserved 14 3.3. Antibacterial activity Our results demonstrated that all studied complexes display antibacterial activity against the bacteria tested especially Gram positive ones. With comparing antibacterial activity of the complexes with those of reference antibiotics, it seems that they have remarkable inhibitory potency against bacteria.Results from antibacterial assessment of the samples and from positive and negative controls are in Tables 2 and 3. The test compounds were dissolved in DMSO at concentrations of 1, 0.1 and 0.01 mgml -1 . DMSO which was used as a solvent was also screened against all bacteria. It has no activity against the bacteria. Generally the antibacterial activity of compounds is attributed mainly to its major components. However, today it is known that the synergistic or antagonistic effect of one compound, even when it is a minor component of mixture has to be considered (Burt, 2004). The complexes reported here showed more activity against some bacteria, than othersat the same identical experimental conditions. This would suggest that the structure of complexes may reduce the polarity of the metal ion mainly. Perhaps a neutral coordination complex may also transport easily from the lipid phase of the bacterial cell membrane and then affected growth and development (Fahmi et al., 1998; Tumer et al., 2007). Composition of the coordination site and the geometry of the tested complexes seemed to be the principal factors that influence antibacterial activity. However, the complexes studied here may be used in treatment of the diseases caused by tested bacteria. Table 2. Antibacterial activity ligand (L) and corresponding complexes (1-6). Compound Concentratio n Inhibition zone (mm) P. v (-) E. c (-) B. c (+) S. a (+) B. m(+) S. m (-) L 1 (mg/ml) 15 ± 0.32 a 10 ± 0.28 a 7 ± 0.00 10 ± 0.11 a 11 ± 0.13 a 14 ± 0.54 a 0.1(mg/ml) 12 ± 0.14 b 9 ± 0.35 b Na 7 ± 0.18 b 8 ± 0.28 b 11 ± 0.22 b 0.01(mg/ml) 7 ± 0.00 c 7 ± 0.00 c Na Na 8 ± 0.54 b 8 ± 0.18 c 1 1(mg/ml) 16± 0.33 a 18 ± 0.16 a 20 ± 0.14 a 21 ± 0.14 a 25 ± 0.12 a 10 ± 0.66 a 0.1(mg/ml) 12 ± 0.35 b 11 ± 0.15 b 17 ± 0.33 b 16 ± 0.34 b 15 ± 0.25 b 8 ± 0.27 b 0.01(mg/ml) 8 ± 0.24c 7 ± 0.00 c 10 ± 0.18 c 10 ± 0.26 c 11 ± 0.35c Na 2 1(mg/ml) 16 ± 0.43 a 30 ± 0.25 a 19 ± 0.26 a 17 ± 0.25 a 16 ± 0.14a 11 ± 0.46 a 0.01(mg/ml) 11 ± 0.24 b 22 ± 0.23 b 13 ± 0.20 b 13 ± 0.25 b 12 ± 0.18 b 8 ± 0.11 b 0.01(mg/ml) 8 ± 0.10 c 14 ± 0.18 c Na Na Na Na 3 1(mg/ml) 16 ± 0.26 a 15 ± 0.26 a 21 ± 0.38 a 17 ± 0.24 a 14 ± 0.10 a 14 ± 0.26 a 0.1(mg/ml) 11 ± 0.18 b 10 ± 0.18 b 14 ± 0.15 b 14 ± 0.00 b 11 ± 0.15 b 8 ± 0.27 b 0.01(mg/ml) 8 ± 0.24 c 7 ± 0.24 c 10 ± 0.24 c 11 ± 0.34 c 8 ± 0.18 c 7 ± 0.00 c 1(mg/ml) 14 ± 0.13 a 13 ± 0.14 a 11 ± 0.16 a 16± 0.13 a 12 ± 0.16 a 14 ± 0.34 a 4 0.1(mg/ml) 11 ± 0.24 b 9 ± 0.21 b 8 ± 0.15 b 11 ± 0.33 b 8 ± 0.23 b 10 ± 0.21 b 0.01(mg/ml) 8 ± 0.15 c 9 ± 0.18 b 7 ± 0.11 c 10 ± 0.11 c 8 ± 0.15 b 8 ± 0.00 c 1(mg/ml) 14 ± 0.16 a 15 ± 0.33 a 13 ± 0.16 a 18 ± 0.25 a 11 ± 0.14 a 14 ± 0.33 a 5 0.1(mg/ml) 10 ± 0.24 b 14 ± 0.15 b 10 ± 0.45 b 13 ± 0.10 b 8 ± 0.26 b 10 ± 0.11 b 0.01(mg/ml) 8 ± 0.21 c 10 ± 0.00 c 8 ± 0.14 c 8 ± 0.14 c Na 8 ± 0.15 c 1(mg/ml) 16 ± 0.12 a 14 ± 0.38 a 14 ± 0.17 a 17 ± 0.34 a 12 ± 0.23 a 13 ± 0.18 a 6 0.1(mg/ml) 12 ± 0.14 b 11 ± 0.35 b 9 ± 0.15 b 15 ± 0.11 b 8 ± 0.16 b 9 ± 0.73 b 0.01(mg/ml) 10 ± 0.45 c 10 ± 0.25 c 8 ± 0.13 c 10 ± 0.11 c 7 ± 0.27 c 7 ± 0.25 c Experiment was performed in triplicate and expressed as mean ± SD. Values with different superscripts within each column (for any bacteria in different concentrations) are significantly different (P < 0.05). Na: no active.
  • 9. Int. J. Curr.Res.Chem.Pharma.Sci. 2(8): (2015):7–16 © 2015, IJCRCPS. All Rights Reserved 15 Table 3. Antibacterial activity of antibiotics as positive controls and DMSO as negative control. Experiment was performed in triplicate and expressed as mean ± SD. Values with different superscripts within each column (for any bacteria in different concentrations) aresignificantly different (P < 0.05). Na: no active Conclusions The present study describes the synthesis and characterization of a new series of Hg(II), Cd(II) and Ag(I) complexes of a monodentate phosphorus ylide. On the basis of the physical–chemical and spectroscopic data we propose that the ligands described herein exhibit monodentate C-coordination to the metal center. In addition, the metal complexes represent significant antibacterial activity, which may help us to design of improved antibacterial agents. Acknowledgments We are grateful to Bu-Ali Sina University for financial support. References Agwara, M.O., Yufanyi, D.M., Foba-Tendo, J.N., Atamba, M.A., Ndinteh, D.T., 2011. Synthesis, characterisation and biological activities of Mn(II), Co(II) and Ni(II) complexes of hexamethylenetetramine. J. Chem. Pharm. Res. 3 (3): 196-204. Awoyinka, O.A., Balogun, I.O., Ogunnowo, A.A., 2007. Phytochemical screening and invitro bioactivity of Cnidoscolus aconitifolius (Euphorbiaceae). J. Med. Plants Res. 3: 63-65. Bennett, P.M., 2008. Plasmid encoded antibiotic resistance: acquisition and transfer of antibiotic resistance genes in bacteria. Br. J. Pharmacol. 153: S347-S357. Burt, S., 2004. Essential oils: their antibacterial properties and potential applications in foods—a review. Int. J. Food Microbiol. 94: 223-253. Christau, H.J., 1994. Synthetic Applications of Metalated Phosphonium Ylides.Chem. Rev. 94: 1299-1313. Fahmi, N., Gupta, I.J., Singh, R.V., 1998. Sulfur bonded palladium(II) and, platinum(II) complexes of biologically potent thioamides. Phosphorus Sulfur Silicon Relat. Elem. 132: 1-8. Holy, N.L., Baenziger, N.C., Flynn, R.M., Swenson, D.C., 1976. The synthesis and structure of mercuric halide complexes of triphenylphosphonium cyclopentadienylide. The first x-ray structure of a mercury cyclopentadienyl. J. Am. Chem. Soc. 98: 7823-7824. Islam, M.S., Farooque, M.A., Badruddoza, M.A.K.E., Mosaddeq, M.A., Alam, M.S., 2002. Antimicrobial and Toxicological Studies of Mixed Ligand Transition Metal Complexes of Schiff Bases. J. Biol. Sci. 2: 797–799. Kalyanasundari, M., Panchanatheswaran, K., Robinson, W.T., Wen, H., 1995. Reactions of benzoylmethylenetriphenylphosphorane with mercury(II) halides: spectral and structural characterization of [(C6H5)3PCHCOC6H5.HgCl2]2.2CH3OH and [(C6H5)3PCHCOC6H5 · HgI2]2. J Organomet Chem 491: 103-109. Kamalakannan, P., Venkappayya, D., 2002. Synthesis and characterization of cobalt and nickel chelates of 5-dimethylaminomethyl-2-thiouracil and their evaluation as antimicrobial and anticancer agents. J. Inorg. Biochem. 90: 22-37. Microorganism Inhibition zone (mm) Gentamicin Penicilli n Nitrofurantion Neomyci n DMSO Proteus vulgaris (−) 28 ± 0.64 NA 18 ± 0.23 21 ± 0.45 NA Escherichia coli (−) NA NA 23 ± 0.33 24 ± 0.16 NA Bacillus cereus (+) 22 ± 0.57 NA 12 ± 0.28 18 ± 0.17 NA Staphylococcus aureus(+) 37 ± 0.21 NA 30 ± 0.22 24 ± 0.28 NA Bacillus megaterium(+) 25 ± 0.44 NA 23 ± 0.46 18 ± 0.26 NA Serratiamarcescens(−) 22 ± 0. 22 NA 18 ± 0.44 25 ± 0.33 NA
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