Synthesis, characterization, and antimicrobial activities of Cu(I), Ag(I), Au(I), and Co(II) complexes with [CH3N(CH2PPh 2)2]

Article abstract of DOI:10.1002/hc.20145

Transition metal complexes of ditertiary aminomethylphosphine ligand, (Ph₂PCH₂)NCH₃ [N, N-bis (diphenylphospinomethyl)aminomethane], dppam, with metal ions which are Ag(I), Au(I), Cu(I), and Co(II) have been synthesized under nitrogen atmosphere by the Schlenk method. [Ag(dppam)₂]NO₃ (1), [Au(dppam) ₂]Cl (2), and [Cu(dppam)₂]Cl (3) complexes have been isolated as colorless solids, whereas [CoCl₂ (dppam)J (4) complex as a blue solid. All complexes have been characterized by atomic absorption, FT-IR, NMR (¹H, ¹³C, 3¹P) spectroscopic, thermogravimetric/differantial thermal analysis (TG/DTA), and elemental analysis techniques. Antimicrobial activity of 1, 2, 3, and 4 were studied in vitro on 13 bacteria and 4 yeasts. The cobalt(II) phosphine complex has shown the best antimicrobial activity in comparison with the other metal complexes.

Full text of DOI:10.1002/hc.20145

Heteroatom Chemistry
Volume 16, Number 6, 2005
S
ynthesis, Characterization, and Antimicrobial
Activities of Cu(I), Ag(I), Au(I), and Co(II)
Complexes with [CH N(CH PPh ) ]
3
2
2 2
1
1
2
Serhan Uru s¸ , Osman Serinda g˘ , and Metin Di g˘ rak
1
Department of Chemistry, Faculty of Science and Literature, University of C¸ ukurova,
0
1330 Adana, Turkey
2
˙
Department of Biology, Faculty of Science and Literature, University of S u¨ t c¸ u¨ Imam,
4
6100 K. Mara s¸ , Turkey
Received 15 February 2005; revised 25 April 2005
ꢁ
type (R
phosphonium salts [R
amines R’NH [1–4].
2
PCH
2
)
2
NR can be obtained by treating the
ABSTRACT: Transition metal complexes of diter-
2
P(CH OH) ]Cl with primary
2
2
tiary aminomethylphosphine ligand, (Ph
2
PCH
2
)NCH
3
2
[
N,N-bis(diphenylphospinomethyl)aminomethane],
The reported studies on antimicrobial and an-
titumoral activities of Ag(I) and Au(I) complexes
using phosphines show
antimicrobial activities [5,6]. It has also been
reported that Au(I) bis(diphosphine) complexes
such as [Au(dppe)
phinoethane) and optically active phosphine-gold(I)
complexes are active against some types of cancer
dppam, with metal ions which are Ag(I), Au(I), Cu(I),
and Co(II) have been synthesized under nitrogen atmo-
a wide spectrum of
sphere by the Schlenk method. [Ag(dppam)
Au(dppam) ]Cl (2), and [Cu(dppam) ]Cl (3) com-
plexes have been isolated as colorless solids, whereas
CoCl (dppam)] (4) complex as a blue solid. All com-
plexes have been characterized by atomic absorption,
2
]NO (1),
3
[
2
2
+
2
]
(dppe = 1, 2-diphenylphos-
[
2
1
13
31
FT-IR, NMR ( H, C, P) spectroscopic, thermogravi-
metric/differantial thermal analysis (TG/DTA), and
elemental analysis techniques. Antimicrobial activity
of 1, 2, 3, and 4 were studied in vitro on 13 bacteria and
[7].
In spite of the researches on the chemistry and
catalytic activities of metal–phosphine complexes,
the biochemistry of aminomethylphosphines hav-
ing P–C–N linkage has not been studied exten-
sively so far. Therefore, our interest in aminomethyl-
phospines has prompted us to synthesize novel
aminomethylphosphine–metal complexes of Au(I),
Ag(I), Cu(I), and Co(II) and to explore some biologi-
cal properties of these complexes.
4
yeasts. The cobalt(II) phosphine complex has shown
the best antimicrobial activity in comparison with the
other metal complexes. ꢀC 2005 Wiley Periodicals, Inc.
Heteroatom Chem 16:484–491, 2005; Published online
in Wiley InterScience (www.interscience.wiley.com). DOI
10.1002/hc.20145
EXPERIMENTAL
INTRODUCTION
Materials and Chemical Reagents
We have shown that a variety of functionalized
chelating ditertiary aminomethylphosphines of the
Chemistry. The metal contents of the com-
plexes were measured by atomic absorption spec-
troscopy on Hitachi 180-80 polarized Zeiman atomic
absorption spectrometer. Elemental analysis was
performed with LECO CHNS 932. Melting points
Correspondence to: Osman Serinda g˘ ; e-mail: osmanser@cu.
edu.tr.
Contract grant sponsor: C¸ ukurova University Research Fund.
ꢀ
c 2005 Wiley Periodicals, Inc.
4
84

Synthesis, Characterization, and Antimicrobial Activities of Cu(I), Ag(I), Au(I), and Co(II) Complexes 485
were determined in open capillary tubes on digital
Synthesis
Gallenkamp melting point apparatus and are un-
corrected. FT-IR spectra were obtained using KBr
pellets with Perkin-Elmer RX1 FT-IR system in the
CH
[PPh
according to [3,4,14]. 1.0 mL Triethylamine (99%)
added to a stirred solution of [PPh (CH OH) ]Cl
(1 g, 3.5 mmol) in 30 mL ethanol (2:1, EtOH:water).
1.8 mL Methylamine (40%) was syringed into the
cloudy solution, and the mixture was refluxed for
1 h. After cooling, the oily product was extracted with
3
N(CH
2
PPh
2
)
2
(dppam). The phosphonium salt,
2
(CH OH)
2
2
]Cl, and dppam ligand were prepared
−1
1
13
31
range 4000–450 cm . H-NMR, C, and P-NMR
◦
6
spectra were recorded at 25 C in DMSO-d and CDCl
on a Varian mercury 200 MHz NMR spectrome-
3
2
2
2
3
1
1
ter. P{ H}-NMR spectra were measured with ref-
erence to an external standard 85% H PO in H O.
3
4
2
Thermogravimetric and differential thermal analy-
sis (TG/DTA) were acquired using a Pyris diamond
TG/DTA Perkin-Elmer thermal analysis and Pyris
dichloromethane and dried over Na
[Ag(dppam) ]NO (1). 0.243 g (0.568 mmol) dp-
pam was added in the Schlenk tube having 10 mL
dichloromethane, and 0.048 g (0.284 mmol) AgNO
2
SO
4
.
2
3
7.0 data-processing system. TG/DTA measurements
were run under nitrogen atmosphere with a tem-
3
◦
−1
◦
perature ramp of 20 C min between 25–700 C.
All chemicals and solvents were purchased from
Merck, Aldrich, Sigma, Fluka, and Riedel-de Ha e¨ n
and used without further purification. All reactions
were carried out under nitrogen atmosphere using
the Schlenk technique.
dissolved in 10 mL ethanol was poured slowly
into dppam solution while stirring. The tube was
wrapped with a folio to protect it from light, and the
mixture was stirred for 2 h. While the solvent vol-
ume was reduced, the white solid started to precipi-
tate and with the addition of diethyl ether completed
the precipitation. The white solid was filtered off and
washed with diethyl ether several times and dried
Bioassay. Antimicrobial activities of the metal
complexes were determined using the agar-disc
diffusion method [8]. These microorganisms were
provided by the Microbiology Laboratory Culture
in vacuo. The product is soluble in CHCl
3
, CH
2
2
Cl ,
DMSO and insoluble in water, ethanol, petroleum
◦
ether, and diethyl ether. mp 240.3 C (decomp.). Yield:
˙
Collection, Department of Biology, S u¨ t c¸ u¨ Imam
0.180 g (62%). Anal. calcd for AgC54
H
54
N
3
P
4
3
O or
University, Turkey. The test materials were purified
and dried as much as possible. The bacteria were
[Ag(dppam) ]NO : C, 63.29; H, 5.31; N, 4.10; Ag,
2
3
10.52. Found: C, 63.01; H, 5.19; N, 4.05; Ag, 10.02
(AAS result). TG/DTA data : No weight loss was ob-
served below decomposition temperature; decom-
◦
first incubated at 37 ± 0.1 C for 24 h in nutrient
broth (Difco), and the yeasts were incubated in
◦
◦
Sabourand dextrose broth (Difco) at 25 ± 0.1 C
position began at 238.11 C and three endothermic
◦
for 24 h. After injecting 0.1 mL cultures of the
bacteria and yeast (prepared as above) into petri
peaks were at around 257.34, 450.27, and 582.78 C.
FT-IR (KBr) : ν 3058–3049 (m, Ar-H); 2972–2768
(m, R-H); 1952, 1894, 1816 (w, monosubstitute Ar-
H); 1582 (w, C C (Ph)), 1484 (m, C H); 1434 (s,
7
6
dishes (9 cm) (10 / for the bacteria and 10 / for the
fungi), 15 mL of Mueller Hinton agar (MHA, Oxoid)
and Sabourand dextrose agar (SDA) (sterilized in a
C C (Ph)); 1408, 1384 (w, CH
3
-N); 1156–1040 (m,
◦
flask and cooled to 45–50 C) were homogeneously
C N (ter-amine)); 750–694 (s, monosubstitute Ar-
−
1
1
6
distributed onto the sterilized petri dishes [9,10].
Sterilized blank paper discs 6 mm in diameter
H); 522–486 (w, P-Ph
2
) cm . H-NMR (DMSO-d ,
◦
2
25 C): δ 7.533–7.024 [m, 40H, 8Ph], 3.584 [d, JHH
-N)], 2.362 [s, 6H, 2(N-CH
ppm. C-NMR (DMSO-d , 25 C): δ 133.696–128.99
=
(Schleicher & Sch u¨ ll no: 2668, Germany) were
8.6 Hz, 8H, 4 (P-CH
2
3
)]
1
3
6
◦
saturated with 800, 1000, and 1200 ꢀg of chemical
samples per disc, then placed onto the agar plates
which had previously been inoculated with the
above organisms [10,11]. The discs injected only
with DMSO were used as control. Blank paper
discs treated with ampicillin, streptomycin, and
[m, Ph], 58.113 [br, P-CH
P-NMR (DMSO-d , 25 C): δ 36.276 [br, Ag-PPh
2
◦
-N], 38.093 [s, N-CH ] ppm.
3
3
1
6
2
]
ppm.
[Au(dppam)
2
]Cl (2). 1.44 g (3.366 mmol) dppam
was added in the Schlenk tube having 10 mL dichlo-
romethane and treated with 0.223 g (0.561 mmol)
˙
nystatin-saturated antibiotics (Eczacıba s¸ ı Ila c¸
Sanayi, Turkey) were used as positive controls.
After the plates combined with the discs were
NaAuCl
4
·2H
2
O dissolved in ethanol. The mixture was
refluxed for 15 min and then stirred for 2 h at room
temperature. The yellow mixture gradually became
colorless. The volume of the mixture was reduced,
addition of diethyl ether completed precipitation,
and the white solid product was filtered off, washed
with diethyl ether several times, and dried in vacuo.
◦
left at 4 C for 2 h, the plates injected with yeast
◦
were incubated at 25 ± 0.1 C for 24 h and
those injected with bacteria were incubated
◦
at 37 ± 0.1 C for 24 h [11–13]. At that time, in-
hibition zones appearing around the discs were
measured and recorded in millimeter.
The product is soluble in CHCl
3
, CH
2
2
Cl , DMSO, and

4
86 Uru s¸ , Serinda g˘ , and Di g˘ rak
insoluble in water, ethanol, petroleum ether, and di-
ethyl ether solvents. mp 195.6 C (decomp.). Yield:
initial dark red color of cobalt(II) solution gradually
turned into blue after stirring of 15 min. After reduc-
ing the volume of the mixture, the blue solid was ob-
tained from the solution and precipitation was com-
pleted with addition of diethyl ether. The product was
filtered off, washed with diethyl ether, and dried in
◦
0.5493 g (90%). Anal. calcd for AuC54
H
54
N
2
4
P Cl : C,
59.65; H, 5.02; N, 2.58; Au, 18.11. Found: C, 59.03;
H, 4.99; N, 2.05; Au, 17.26 (AAS result). TG/DTA
data : no weight loss was observed below decomposi-
◦
tion temperature; decomposition began at 199.85 C,
vacuo. The solid is soluble in CHCl
3
, CH
2
2
Cl , DMSO
and three endothermic peaks were at around 248,
solvents, and insoluble in water, ethanol, petroleum
ether, and diethyl ether. mp 105.9 C. Yield: 0.134 g
◦
◦
302, and 342 C. FT-IR (KBr) : ꢁ 3124–3046 (m, Ar-
H); 2916–2784 (s, R-H); 1956, 1880, 1804 (w, mono-
substitute Ar-H); 1582, 1568 (w, C C (Ph)), 1474
(85%). Anal. calcd For CoC27
H
27NP
2
Cl : C, 58.19; H,
2
4.88; N, 2.52; Co, 10.57. Found: C, 58.08; H, 4.03;
N, 2.12; Co, 10.01 (AAS result). TG/DTA data: no
weight loss was observed below decomposition tem-
(m, C H); 1434 (s, C C (Ph)); 1384, 1274 (w, CH
3
-
N); 1094 (m, C N (ter-amine)); 738–692 (s, mono-
−
1
1
◦
substitute Ar-H); 534–484 (w, P-Ph
2
) cm . H-NMR
, 25 C): δ 7.135–6.711 [m, 40H,
-N)], 2.193 [s, 6H, 2
perature; decomposition began at 123.22 C and three
6
◦
(
8
DMSO-d + CDCl
3
endothermic peaks at around 153.59, 292.73, and
◦
Ph], 3.28 [br, 8H, 4 (P-CH
2
549.54 C. FT-IR (KBr) : ꢁ 3054 (m, Ar-H); 2940–2788
1
3
6
◦
(N-CH
3
)] ppm. C-NMR (DMSO-d + CDCl
3
, 25 C):
(s, R-H); 1960, 1894, 1814 (w, monosubstitute Ar-H);
1588 (w, C C (Ph)), 1482 (m, C H); 1437 (s, C C
δ 132.793–128.006 [m, Ph], 61.992 [s, P-CH
2
-N],
3
1
6
◦
3
8.163 [s, N-CH
δ 52.941 [s, Au-PPh
Cu(dppam) ]Cl (3). 1.161 g (3.768 mmol) dppam
was dissolved in the Schlenk tube using 10 mL
dichloromethane. 0.0957 g (0.628 mmol) CuCl
O dissolved in 10 mL ethanol was poured slowly
3
] ppm. P-NMR (DMSO-d , 25 C):
(Ph)); 1324–1274 (w, CH
3
-N); 1140–1026 (m, C N
2
] ppm.
(ter-amine)); 742–692 (s, monosubstitute Ar-H); 568–
−
1
1
6
◦
[
2
510 (w, Co-PPh
2
) cm . H-NMR (DMSO-d , 25 C): δ
-N],
7.675–7.211 [m, 20H, 4Ph], 3.617 [br, 4H, 2CH
2
1
3
6
2
·
2.420 [br-s, 3H, N-CH
25 C): δ 130.411–125.822 [m, Ph], 59.6 [br, P-CH
3
] ppm. C-NMR (DMSO-d ,
◦
2H
2
2
-
3
1
6
◦
into dppam solution while stirring. The blue color of
copper(II) solution gradually became colorless. Hav-
ing reduced the volume of solution and added diethyl
ether, the solid was obtained which was filtered off,
washed, with diethyl ether several times and dried
N], 28.5 [s, N-CH
δ 51.877 [s, Co-PPh
3
] ppm. P-NMR (DMSO-d , 25 C):
] ppm.
2
RESULTS AND DISCUSSION
Synthesis
in vacuo. The product is soluble in CHCl
3
, CH
2
2
Cl ,
DMSO, and insoluble in water, ethanol, petroleum
◦
ether, and diethyl ether mp 160.9 C. Yield: 0.485 g
Dppam ligand was synthesized by treating phospho-
nium salt with primary amines according to the
Mannich reaction, and the transition metal com-
plexes of the aminomethylphosphine ligand were
prepared under nitrogen atmosphere using Schlenk
techniques as shown in Scheme 1 [1].
(
81%). Anal. calcd for CuC54
H, 5.71; N, 2.94; Cu, 6.66. Found: C, 67.11; H,
.19; N, 2.90; Cu, 6.10 (AAS result). TG/DTA data:
H
54
N
2
P
4
Cl : C, 67.99;
5
no weight loss was observed below decomposition
◦
temperature; decomposition began at 176.2 C, and
three endothermic peaks were at around 232.97,
The metal complexes 1,2,3, and 4 were ob-
◦
336.86, and 580.05 C. FT-IR (KBr) : ꢁ 3064–3053
tained by the reaction of dppam in CH
2
2
Cl with
(
m, Ar-H); 2940–2788 (s, R-H); 1956, 1888, 1812 (w,
monosubstitute Ar-H); 1584 (w, C C (Ph)), 1482 (m,
C H); 1434 (s, C C (Ph)); 1408 (w, CH -N); 1094
m, C N (ter-amine)); 740–696 (s, monosubstitute
appropriate amount of metal salts dissolved in
absolute ethanol, respectively. Since the metal–
aminomethylphosphine complexes are insoluble in
diethyl ether, the products can easily be separated
from the mixture with the addition of diethyl ether.
Due to the fact that aminomethylphosphines can eas-
ily be oxidized, Au(III) and Cu(II) ions were reduced
to Au(I) and Cu(I) during the reaction by using ex-
cess dppam ligand in synthesis of the complexes 2
and 3. The reduction of Au(III) to Au(I) and Cu(II)
to Cu(I) was monitored with color changes from yel-
low to colorless and from blue to colorless, respec-
tively, as expected. Even though the solid state of
the complexes are stable in air, they all can decom-
pose in a solution having small quantity of water and
oxygen.
3
(
−1 1
Ar-H); 552–488 (w, Cu-PPh ) cm . H-NMR (DMSO-
d , 25 C): δ 7.492–7.146 [m, 40H, 8Ph], 3.832 [d-br,
8
NMR (DMSO-d , 25 C): δ 133.211–128.7 [m, phenyl],
5
NMR (DMSO-d , 25 C): δ 50.965 [s, Cu-PPh
ppm.
CoCl
was added into the Schlenk tube having 10 mL dich-
loromethane. 0.0775 g (0.283 mmol) CoCl O dis-
solved in 10 mL ethanol was poured slowly into dp-
pam solution while stirring. During the reaction, the
2
6
◦
1
3
H, 4 (P-CH
2
-N)], 2.050 [s, 6H, 2 (N-CH )]] ppm. C-
3
6
◦
3
1
9.274 [br, P-CH
2
6
-N], 30.590 [s, N-CH
3
] ppm. P-
◦
2
]
[
2
(dppam)] (4). 0.121 g (0.283 mmol) dppam
2
·6H
2

Synthesis, Characterization, and Antimicrobial Activities of Cu(I), Ag(I), Au(I), and Co(II) Complexes 487
SCHEME 1
Characterization
which show C–N–C stretching peaks around 1150–
−
1
1
040 cm for tertiary amine. Aromatic C-H stretch-
−
1
In order to characterize the metal complexes, AAS,
FT-IR, NMR, TG/DTA, and elemental analysis tech-
niques were used.
ing band has been found at about 3058–3042 cm ;
the peaks around 1816–1952 cm and 694–750 cm
−
1
−1
are assigned for monosubstitute benzene whereas
1
−1
The examination of H-NMR spectra of the com-
bands in the range of 2940–2780 cm
aliphatic C-H stretching [14,28]
are for
plexes showed that the aromatic protons of the
phenyl ring substituted on phosphorus have the
chemical shift value (δ) in a range of 6.8–7.6 ppm.
Elemental analysis for C, H, N and atomic ab-
sorption spectroscopy for metal contents show the
basic formulas of the complexes. Based on the spec-
tral and analytical data, metal to ligand ratio has
been found as 1:2 for the complexes 1, 2, and 3
and 1:1 for the complex 4. Because of the fact that
we could not obtain suitable crystals of the synthe-
sized complexes for further structural characteriza-
tion with single crystal X-ray crystallography, we
evaluated the structures of the complexes by using
sufficient analytical and spectroscopic data. Since
metal ions of Ag(I), Au(I), and Cu(I) are diamag-
netic, their expected geometry is distorted tetrahe-
dral whereas paramagnetic Co(II) complex is ex-
pected to be as square planar. Computer drawing of
complex 1, 2, 3 on Chem Draw 3D based on analyti-
cal data showed tetrahedral geometry of metal center
having P–M–P bond angles consistent with those of
reported tetrahedral Au(I), Ag(I), Cu(I) complexes as
shown Fig. 1 [6,24,29,30].
The characteristic P-CH
2
-N protons and N-CH pro-
3
tons of aminomethyl phoshines of the metal com-
plexes are observed around 3.6 ppm and 2.2 ppm,
respectively which are consistent with those of re-
ported data [1–4].
3
1
P-NMR spectra of the complexes showed
more shielded signals compared with the free
aminomethylphosphine ligand observed at −27.53
ppm according to the literature [3]. Table 1 shows
the coordination shift (δ) of the complexes along
with the chemical shifts of the complexes. The co-
ordination shift values of the complexes (ꢀ), which
can be defined by ꢀ = δ (complex) − δ (free ligand),
vary depending on the metal centers and the lig-
and itself. The values of ꢀ have been correlated to
many metal phosphine complexes [13]. The specific
3
1
1
P-{ H} NMR peaks of the complexes have been
observed at 36.276 (br), 52.941 (s), 50.965(s), and
5
1.877(s) ppm for 1, 2, 3, and 4, respectively. These
Ionic structures of 1, 2, 3, and 4 complexes were
tested with simple qualitative tests. According to the
chemical shifts prove that the complexes were ob-
tained as expected, in comparison with the literature
−
results of these tests, Cl ions are not in coordina-
−
[14–28]. The silver(I) complex is expected to show Ag
tion sphere for 1, 2, and 3, whereas Cl ions have
coupling to P nuclei. However, the solution NMR has
shown a broad peak of P atoms at room temperature.
The metal aminomethylphosphine complexes
were further characterized by FT-IR spectra. Table 1
also presents the FT-IR data of the complexes
coordinated to Co(II) for the complex 4.
All complexes have shown three endothermic
peaks in TG/DTA results. Ag(I) complex was sta-
◦
ble at the temperature of 238.11 C, and decomposi-
tion started at this temperature and was completed

4
88 Uru s¸ , Serinda g˘ , and Di g˘ rak

Synthesis, Characterization, and Antimicrobial Activities of Cu(I), Ag(I), Au(I), and Co(II) Complexes 489
FIGURE 1 Tetrahedral Au(I), Ag(I), Cu(I) complexes (a) and square planar Co(II) complex (b).
◦
at 280 C. The second endothermic peak began at
complexes have been found inactive at the concen-
tration of 800 ꢀg/disc and 1000 ꢀg/disc against tested
bacteria and fungi respectively, whereas the Co(II)
phosphine complex (4) has shown moderate activ-
ity at 1000 ꢀg/disc. The compounds 1,2, and 3 are
moderately active at the concentration 1200 ꢀg/disc;
however, the compound 4 showed the best activity
when compared with 1, 2, and 3. Cobalt complex
has almost shown similar activity against some of
the bacteria when compared with the standard an-
tibiotics like ampicillin and streptomycin. Activity
of cobalt complex against some fungi has been mea-
sured and is very close in nystatin (an antifungal).
The results are useful to explaining the dppam
complexes of Ag(I), Au(I), Cu(I) which are thought
of as inert complexes in terms of microbiological ac-
tivities, whereas Co(II) complex shows labile prop-
erty. This differentiation could be explained as due
to having less bulky geometry of the square pla-
nar Co(II) complex. The structural characterization
showed that complexes 1, 2, and 3 with bidentate
tertiary aminomethylphosphine ligand, dppam, are
sterically crowded more than the complex 4. There-
fore, the microbiological activity of the compound 4
is different from 1, 2, and 3.
◦
◦
4
33.86 C and finished at 471.85 C. The last endother-
◦
◦
mic peak was between 569.72 C and 601.86 C.
The decomposition of the complex of Au(I) be-
gan at 179.85 C and continued to 265 C. Other two
endothermic peaks were respectively between 299.7–
19.5 C and 325.8–405.9 C.
Cu(I) complex decomposed at the temperature
of 176.2 C, and the first endothermic step finished
at 249.54 C. The second step of decomposition was
at 250.01–470.81 C when a great deal of mass was
removed. The last peak started at the temperature
◦
◦
◦
◦
3
◦
◦
◦
◦
of 573.22 C and completed at the temperature of
◦
5
90.93 C.
The endothermic peaks of Co(II) were around
23.22–177.02 C, 182.09–291.72 C, and 544.47–
59.7 C.
◦
◦
1
5
◦
Antimicrobial Activity
Growth inhibitory activity of the chemical materials
was tested against 13 bacteria (e.g., Corynebacterium
xerosis UC9165, Bacillus brevis FMC 3, Bacillus
megaterium DSM 32, Bacillus subtilis IMG 22, My-
cobacterium smegmatis RUT, Pseudomonas aerugi-
nosa DSM 50071, Staphylococcus aureus Cowan 1,
Klebsiella pneumoniae FMC 5, Klebsiella oxytocica
A, Enterococcus faecalis CR 25, Micrococcus luteus
LA 2971, Escherichia coli ATCC 25922, and Yersinia
enterocolitica CR 38) and four fungi (Kluyveromyces
fragilis, Rhodotorula rubra, Saccharomyces cerevisiae
WET 136, and Candida albicans). The homogeneous
solutions of the complexes were prepared in DMSO
which showed no activity as a solvent in these assays.
Compounds were initially dissolved in DMSO in the
minimal volume, then serially diluted with media to
the concentration, so there was very minimal resid-
ual DMSO in the assayed medium.
CONCLUSIONS
The complexes Ag(I), Au(I), Cu(I), and Co(II) with
bidentate tertiary aminomethylphosphine ligand
(dppam) have been synthesized and characterized
by using spectroscopic, thermal, and microanalyt-
3
1
1
ical methods. P-{ H}NMR spectra of the metal
complexes have indicated that coordination of
aminomethylphosphine ligand to metal center gives
deshielded chemical shift value compared with free
ligand.
Antimicrobial activities of the metal complexes
were determined using the agar-disc diffusion
method. Ampicillin, streptomycin, and nystatin-
saturated antibiotics were used as positive controls.
Investigation of the antimicrobial activity of the
complexes showed almost similar results except for
complex 4. As given in Table 2, Cu(I), Ag(I), and Au(I)

4
90 Uru s¸ , Serinda g˘ , and Di g˘ rak
TABLE 2 Antimicrobial Activities of 1, 2, 3, and 4 and Antibiotics for Positive Control
Inhibition Zone (mm)
1
000 µg Complex/disc
1200 µg Complex/disc
Standard Antibiotics
Microorganisms
1
2
3
4
1
2
3
4
A10
S10
N30
Corynebacterium xerosis
Bacillus brevis
Bacillus megaterium
Bacillus subtilis
Mycobacterium smegmatis
Pseudomonas aeruginosa
Staphylococcus aureus
Klebsiella pneumoniae
Klebsiella oxytocica
Enterococcus faecalis
Micrococcus luteus
Escherichia coli
Yersinia enterocolitica
Kluyveromyces fragilis
Rhodotorula rubra
Saccharomyces cerevisiae
Candida albicans
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
7
11
10
8
10
8
7
7
16
8
8
9
10
7
7
8
7
8
7
9
8
7
7
8
7
7
7
8
7
7
7
–
7
7
7
10
8
7
–
10
–
7
9
8
–
–
7
12
14
11
15
19
10
16
17
15
16
33
11
13
–
10
16
17
18
15
13
21
16
14
17
–
–
17
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
15
14
18
16
8
7
8
9
8
8
7
8
–
7
8
7
10
9
12
19
15
12
15
13
11
12
20
12
14
11
7
7
–
8
16
12
–
–
–
10
7
9
–
–
Standard antibiotic discs; A10: ampicillin (10 µg/disc); S10: streptomycin (10 µg/disc); N30: nystatin (antifungal, 30 µg/disc).
At concentrations of 800 ꢀg/disc and 1000 ꢀg/disc,
the complexes 1–3 are inactive against tested bacte-
ria and fungi, whereas the compound 4 is more active
than others. The compounds 1, 2, and 3 have shown
moderate activity at the concentration of 1200 ꢀg/
disc; however, the compound 4 has shown the best
activity when compared with 1, 2, and 3 and similar
activity as those of antibiotics.
[8] C¸ etin, A.; Cansız, A.; Di g˘ rak, M. Heteroatom Chem.
003, 14, 4, 345–347.
2
[
9] Cansız, A.; Servi, S.; Koparır, M.; Altınta s¸ , M.; Di g˘ rak,
M. J Chem Soc Pak 2001, 23(4), 237–240.
[
10] T u¨ mer, M.; K o¨ ksal, H.; Serin, S.; Di g˘ rak, M. Trans Met
Chem 1999, 23, 13–17.
[11] Bradshaw, L. J. Laboratory of Microbiology, 4th ed.;
Saunders College Publishing: Philadelphia, PA, 1992;
pp. 435.
12] Collins, C. H.; Lyne, P. M.; Grange, J. M. Microbiolog-
ical Methods, 6th ed.; Butterworths: London, 1989;
pp. 410.
13] Garrau, P. E. Chem Rev 1981, 81, 229–250.
14] Serinda g˘ , O. Ph.D. Thesis, Department of Chemistry,
University of Leicester, Leicester, UK, 1993.
15] Effendy, Hanna, J. V.; Marchetti, F.; Martini,
D.; Pettinary, C.; Pettinary, R.; Skelton, B. W.;
White, A. H. Inorg Chim Acta 2004, 357, 1523–
[
ACKNOWLEDGMENTS
[
[
We would like to thank Prof. Dr. Ya s¸ ar G o¨ k and Mira c¸
Nedim Mısır for NMR measurements. The authors
also are thankful Research Fund of C¸ ukurova Uni-
versity for financial support to this project.
[
[
1
537.
16] Shi, Ji-Cheng; Chen, Lin-Ji; Huang, Xiao-Ying; Wu,
Da-Xu; Kang, Bei-Sheng J Organomet Chem 1997,
REFERENCES
5
35, 17–23.
[
[
[
[
[
[
[
1] Fawcett, J.; Kemmit, R. D. W.; Russel, D. R.; Serindag,
O. J Organomet Chem 1995, 486, 171–176.
2] Serindag, O.; Kemmit, R. D. W.; Fawcett, J.; Russel,
D. R. Trans Met Chem 1995, 20, 548–551.
[17] Nomiya, K.; Noguchi, R.; Ohsawa, K.; Tsuda, K.; Oda,
M. J Inorg Biochem 2000, 78, 363–370.
[18] Bachert, I.; Braunstein, P.; Mccart, M. K.; De Biani,
F. F.; Laschi, F.; Zanello, P.; Kickelbick, G.; Schubert,
U. J Organomet Chem 1999, 573, 47–59.
[19] Ebsworth, E. A. V.; Rankin, D. W. H.; Cradock, S.
Structural Methods in Inorganic Chemistry, Nuclear
Magnetic Resonance and Vibrational Spectroscopy,
2nd ed.; Blackwell Scientific: Oxford, 1991: pp. 28–
102, 216–246, 173–246.
[20] Fawcett, J.; Hoye, P. A. T.; Kemmit, R. D. W.; Law,
D. J.; Russel, D. R. J Chem Soc, Dalton Trans 1993,
2563–2568.
3] Serindag, O. Synth React Inorg Met-Org 1997, 27, 69–
7
6.
4] Serindag, O.; Kemmit, R. D. W.; Fawcett, J.; Russel
D. R. Trans Met Chem 1999, 24, 486–491.
5] Esp o´ sıto, B. P.; Najjar, R. Coord Chem Rev 2002, 232,
1
37–149.
6] McKeage, M. J.; Maharaj, L.; Berners-Price, S. J.
Coord Chem Rev 2002, 232, 127–135.
7] (a) Novelli, F.; Recine, M.; Sparatore, F.; Juliano,
C. Il Farmaco 1999, 54, 232–236; (b) Leung, P. H.;
Ha Chan, S.; Song, Y., PCT WO 01/77121.
[21] Westmark, G.; Kariis, H.; Persson, I.; Liedberg, B. Col-
loids Surf A 1999, 150, 31–43.

Synthesis, Characterization, and Antimicrobial Activities of Cu(I), Ag(I), Au(I), and Co(II) Complexes 491
[
[
22] Hollatz, C.; Schier, A.; Schmidbaur, H. Inorg Chim
[26] Berners, P. S.; Giovenella, Al J.; Faucette, F.; Sadler,
P. J. J Inorg Biochem 1988, 4, 285–295.
[27] Wang, M.; Yu, X.; Shi, Z.; Qian, M.; Jin, K.; Chen, J.;
He, R. J Organomet Chem 2002, 645, 127–133.
[28] Cingolani, A.; Effendy; Marchetti, F.; Pettirari, C.;
Skelton, B. W.; White, A. H. J Chem Soc, Dalton Trans
1999, 4047–4055.
[29] Law, D. J. Ph.D. Thesis, Leicester University, Leices-
ter, UK, 1990.
[30] Lewis, J. S.; Zweit, J.; Blower, P. J. Polyhedron 1998,
17, 513–517.
Acta 2000, 300–302, 191–199.
23] Coles, S. C.; Faulds, P.; Hursthouse, M. B.; Kelly,
D. G.; Toner, A. J. Polyhedron 2000, 19, 1271–
1
278.
[
[
24] Berners, S. J.; Bowen, R. J.; Galettis, P.; Mckeage,
M. J. Coord Chem Rev 1999, 185–186, 823–
8
36.
25] Berners-Price, S. J.; Mirabelli, C. K.; Jhonson, R. K.;
Mccabe, F. L.; Sadler, P. J.; Faucette, L. F. Inorg Chem
1
987, 26, 3383–3387.