Synthesis and characterization of some transition metal complexes of thiosemicarbazones derived from 2-acetylpyrrole and 2-acetylfuran

Article abstract of DOI:10.1081/SIM-200059215

Copper(II), nickel(II), palladium(II), platinum(II), and silver(I) complexes of 2-acetylpyrrole thiosemicarbazone (H₂L¹) and copper(II), nickel(II), platinum(II) and zinc(II) complexes of 2-acetylfuran thiosemicarbazone (HL²

Full text of DOI:10.1081/SIM-200059215

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Synthesis and Characterization of some Transition
Metal Complexes of Thiosemicarbazones Derived from
2
‐acetylpyrrole and 2‐acetylfuran
a a
Nabil S. Youssef & K. H. Hegab
a
Inorganic Chemistry Department , National Research Center , Dokki, Giza, Egypt
Published online: 15 Feb 2007.
To cite this article: Nabil S. Youssef & K. H. Hegab (2005) Synthesis and Characterization of some Transition Metal Complexes
of Thiosemicarbazones Derived from 2‐acetylpyrrole and 2‐acetylfuran, Synthesis and Reactivity in Inorganic, Metal-Organic,
and Nano-Metal Chemistry, 35:5, 391-399, DOI: 10.1081/SIM-200059215
To link to this article: http://dx.doi.org/10.1081/SIM-200059215
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Synthesis and Reactivity in Inorganic, Metal-Organic and Nano-Metal Chemistry, 35:391–399, 2005
Copyright # 2005 Taylor & Francis, Inc.
ISSN: 0094-5714 print/1532-2440 online
DOI: 10.1081/SIM-200059215
Synthesis and Characterization of some Transition Metal
Complexes of Thiosemicarbazones Derived from
2
-acetylpyrrole and 2-acetylfuran
Nabil S. Youssef and K. H. Hegab
Inorganic Chemistry Department, National Research Center, Dokki, Giza, Egypt
EXPERIMENTAL
Copper(II), nickel(II), palladium(II), platinum(II), and
silver(I) complexes of 2-acetylpyrrole thiosemicarbazone (H L ) Synthesis of the Ligands
1
2
1
The ligands H L and HL (Figure 1) were prepared bymixing
2
and copper(II), nickel(II), platinum(II) and zinc(II) complexes of
2
characterized by conductance, electronic, infrared, magnetic
2
2
-acetylfuran thiosemicarbazone (HL ) have been prepared and
1
.82g (20 mmol) of thiosemicarbzide with 2.18g (20mmol)
1
and H NMR spectral measurements in addition to elemental
and thermogravimetrical analyses. Square-planar structures are
of 2-acetylpyrrole or 2.20g (20 mmol) of 2-acetylfuran in
50 mL of methanol. The mixtures were then stirred for 12
1
1
1
2
suggested for the H
Pt(II), whereas octahedral structures proposed for the HL com-
2
L complexes of Cu(II), Ni(II), Pd(II) and and 1/2 h, in case of ligands H L and HL , respectively,
2
2
when the solid ligands precipitated. The solids were filtered,
washed with methanol, and finally dried in a vacuum desiccator
over anhydrous CaCl . The yields were 2.54 g (69.78%) and
plexes of Cu(II) and Ni(II); the Zn(II) and Ag(I) complexes are
1
2
tetrahedral. Moreover, the results showed that the ligand H L
2
2
is bidentate in all of its complexes, and the ligand HL is either
mono-, di- or tridentate.
1
2
3.21 g (87.70%) for the ligands H L and HL , respectively.
2
Synthesis of the Metal Complexes
Keywords Z–acetylpyrrole, Z–acetylfuran, thiosemicarbazones,
transition metal complexes
1
L )Cl
2
O, [Ni(L )(H
.
] H
The complexes [Ni(H
O)
2 2
2
2
2
1
Cl] 3H O, [Ag(H L )(H O)NO ] 2H O and [Cu(HL )
2
.
.
2
2
2
3
2
.
(H O)Cl ] H O were prepared by mixing an aqueous
2 2 2
.
solution (10 mL) of the metal salt (2.5 mmol of NiCl2 6H O,
2
.
AgNO or CuCl 2H O, respectively) with a warm methanol
3
2
2
INTRODUCTION
1
2
solution (ꢀ408C) (50 mL) of the ligands H L or HL
2
Thiosemicarbazone derivatives and their metal complexes
have extensive biological properties such as antitumor
1
2.5 mmol). The [Pt(H L )Cl ] 4H O complex was prepared
.
(
by the same method using an aqueous solution (20 mL) of
2
2
2
(
Belicchi et al., 1999; Kovala-Demertzi et al., 1997; Kovala-
Demertzi et al., 2001; Quiroga et al., 1999; Tarasconi et al.,
000), fungicidal (Bermejo et al., 1999; Jouad et al., 2001a),
platinum(II) chloride (0.8 mmol) and methanol solution
1
(
ꢀ408C) (20 mL) of the ligand H L (0.8 mmol).
2
2
1
The complexes [Cu(H L ) ]Cl 5H O and [Zn(HL ) Cl ]
2
.
2
2
2
2
2
2
bactericidal (Bindu et al., 1999), and antiviral (Tarasconi
et al., 2000) activity. We have previously described the com-
plexes formed between chromone thiosemicarbazones and
some transition metal ions (Youssef et al., 2003). We report
here the synthesis and the characterization of complexes of
were synthesized by mixing an aqueous solution (10 mL) of
.
the metal salt (2.5 mmol of CuCl2 2H O or ZnCl , respectively)
2
2
with a warm methanol solution (ꢀ408C) (50 mL) of the ligands
1
H L or HL (5 mmol). The complexes [Pd(H L ) ]Cl 2H O
2
1
.
2
2
2
2
2
2
and [Pt(L ) ] were prepared by the same method using
2
2
-acetylpyrrole thiosemicarbazone with Cu(II), Ni(II), Pd(II),
aqueous solutions (20 mL) of palladium chloride or platinum(II)
chloride (0.8 mmol) and methanol solution (ꢀ408C) (50 mL) of
Pt(II), and Ag(I) ions and those of 2-acetylfuran thiosemicarba-
zone with Cu(II), Ni(II), Pt(II) and Zn(II) ions.
1
the ligands H L or HL (1.6 mmol).
2
2
For the Pd(II) and Pt(II) compounds, stock solutions of
2
2
22
.04 M [PdCl4] and [PtCl4] were first prepared following
0
the procedure described in the literature (Kovala-Demertzi
et al., 2000).
Received 11 August 2004; accepted 10 February 2005.
Address correspondence to N. S. Youssef, Inorganic Chemistry
Department, National Research Center, Dokki, Giza, Egypt. E-mail:
nabilyoussef@hotmail.com
The reaction mixture was then gently refluxed with constant
stirring for a time depending on the transition metal salt used.
391

3
92
N. S. YOUSSEF AND K. H. HEGAB
aqueous-methanol
1
1
MCl2 þ2H2L ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ ꢀꢀ! ½MðH2L Þ ꢁCl2 ꢂxH2O
2
M ¼ CuðIIÞ;ðx ¼ 5Þ;
PdðIIÞ;ðx ¼ 2Þ
aqueous-methanol
AgNO þH2L ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ ꢀꢀ! ½AgðH2L ÞðH2OÞNO3ꢁ
1
1
3
ꢂ2H O
2
aqueous-methanol
2
2
CuCl þHL ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ ꢀꢀ! ½CuðHL ÞðH OÞCl ꢁꢂH O
2
2
2
2
aqueous-methanol
FIG. 1. Structure of the ligands.
2
2
NiCl2 þHL ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ ꢀꢀ! ½NiðL ÞðH2OÞ Clꢁꢂ3H2O
2
þHCl
The resulting precipitates were filtered, washed with methanol,
then with diethyl ether, and dried over anhydrous CaCl2.
aqueous-methanol
2
2
ZnCl þ2HL ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ ꢀꢀ! ½ZnðHL Þ Cl ꢁ
2
2
2
aqueous-methanol
2
2
PtCl2 þ2HL ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ ꢀꢀ! ½PtðL Þ ꢁþ2HCl
Physical Measurements
2
The ligands and their complexes were analyzed for C, H, N,
S, Cl, and M contents at the Microanalytical Laboratory,
Faculty of Science, Cairo University, Egypt. The metal ion
contents of the complexes were also determined (Holzbecher
et al., 1976; Vogel, 1978; Welcher, 1958) by previously
reported methods (McDonald and Sirichanya, 1969; Youssef,
The elemental and, in some cases, the thermogravimetric
analyses of the ligands and the solid complexes, listed in
Tables 1 and 2, showed that the stoichiometry of the complexes
obtained is 1:1 and 1:2 (metal:ligand) for both of the two
1
2
ligands H L and HL .
2
2
were measured using KBr discs with a Jasco FT/IR 300E
000). IR spectra of the ligands and their metal complexes
Infrared Spectra
The significant IR bands of the ligands and their metal com-
plexes and their assignments are given in Table 3. The absence
21
of bands in the 2000–2500 cm region (Carballo et al., 2001)
Fourier transform infrared spectrophotometer covering the
2
1
21
range 400–4000 cm
using polyethylene-sandwiched Nujol mulls on a Perkin
and in the 500–100 cm
region
due to n(S–H) in most spectra of the complexes suggests that
these ligands exist mainly in the thione form. However, the
1
Elmer FT-IR 1650 spectrophotometer. H NMR spectra of
the ligands and some of their complexes were recorded in
DMSO-d using a Jeol EX-270 MHz NMR spectrophotometer
2
spectrum of [Cu(HL )(H O)Cl ] H O exhibits a n(S–H)
.
2
2
2
6
21
band at 2120 cm , which is a good evidence that the ligand
from 0–14 ppm with TMS as an internal standard. The elec-
tronic spectra of the ligands and their complexes were
obtained in Nujol mulls and in saturated DMF or DMSO sol-
utions using a Shimadzu UV–240 UV-visible recording spec-
trophotometer. Thermogravimetric analyses of the investigated
complexes were carried out using DTA-7 and TGA-7 Perkin
Elmer 7 series thermal analysis systems. The mass losses
were measured in nitrogen atmosphere from ambient tempera-
2
HL readily converts to the thiol form, without deprotonation,
on coordination with the Cu(II) ion. The bands due to n(CS)
21
and n(CS) þ n(CN) at 750–920 and 1280–1390 cm
,
respectively, in the free ligands H L and HL are either
1
2
2
shifted, split, or disappeared in all of their complexes, indicat-
ing the participation of the S atom in complex formation (John
et al., 2002). The presence of a new band due to n (M–S)
21
1
2
(Fostiak et al., 2002) at 300–408 cm in the H L and HL
2
2
1
ture up to 8008C at a heating rate of 108C min . Molar con-
ductivities in DMF or DMSO at 258C were measured using a
model CM-1K-TOA Company (Japan) conductivity meter.
Magnetic moments at 258C were determined using the Gouy
complexes is another indication of the involvement of the
S atom in coordination. Moreover, coordination of the azo-
methine N to the metal ion is suggested by the shift of the
n (C 55 N) band (Kovala-Demertzi et al., 2001) and the occur-
rence of the n(N–N) band at higher wave numbers in all of
method with Hg[Co(SCN) ] as calibrant.
4
2
the studied complexes except for the [Zn(HL ) Cl ] complex.
2
2
Coordination of the azomethine N is also consistent with the
RESULTS AND DISCUSSION
The formation of the metal chelates of the ligands H L and
2
presence of a band at 332–412 and 560–600 cm in case of
1
1
2
1
2
and HL complexes, respectively, except for the
2
HL is expressed by the following chemical equations:
H
2
L
Cu(HL )(H O)Cl ] H O complex, which are assignable to
2
.
[
n(M–N) for these complexes (West et al., 1995).
2
2
2
aqueous-methanol
1
1
The significant displacement of the frequency of the furan
ring breathing and n(C–O–C) vibrations (Jouad et al., 2002)
MCl2 þH2L ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ ꢀꢀ! ½MðH2L ÞCl2ꢁꢂnH2O
M ¼ NiðIIÞ;ðn ¼ 1Þ;
PtðIIÞ;ðn ¼ 4Þ
2
in case of the [Ni(L )(H O) Cl] 3H O and [Cu(HL )
2
.
2
2
2
.
(H O)Cl ] H O complexes is explicit evidence for the
2 2 2

TABLE 1
Analytical and physical data of the ligands H L and HL and their metal complexes
1
2
2
M.p.
(D.p.)
(8C)
Analysis (%)/found (calcd.)
Molar
conductance
Yield
(%)
2
L (V cm mol
1
2
21
Complexes
FW
182
Color
C
H
N
S
CI
M
)
m
1
Ligand H L C H N S
70
88
79
77
85
90
82
80
89
78
71
Reddish
brown
Dark
213
45.90
5.62
29.97
18.17
2
7 10 4
(46.15) (5.49) (30.77) (17.58)
45.52 4.77 22.73 17.64
(45.90) (4.92) (22.29) (17.49)
28.17 5.10 19.21 10.65
2
Ligand HL C H N OS
183
(160–165)
170–180
170
7
9 3
yellow
Brown
.
Cu(H L ) ]Cl 5H O
[
588.55
329.69
577.40
520.08
11.90
11.13
85.0
8.7
2
1 2
2
2
C H Cl CuN O S
8 5 2
(28.54) (5.10) (19.03) (10.87) (12.06) (10.80)
25.39 3.78 17.13 9.85 21.21 17.97
(25.48) (3.64) (16.98) (9.71) (21.54) (17.80)
29.41 4.00 19.63 10.82 12.45 18.27
(29.09) (4.16) (19.40) (11.08) (12.30) (18.43)
16.21 3.51 10.60 6.12 13.43 37.42
(16.15) (3.46) (10.77) (6.15) (13.65) (37.51)
20.61 3.98 17.51 8.02
(20.70) (3.94) (17.25) (7.88)
32.94 3.62 16.81 12.85
1
4
30
2
1
Ni(H L )Cl ] H O
.
[
C H Cl N NiOS
Brown
2
2
2
7
12
2 4
1
Pd(H L ) ]Cl 2H O
.
[
Reddish
brown
Brown
260–270
240–250
170–180
223
75.8
14.2
36.0
8.2
2
2
2
2
C H Cl N O PdS
2
1
4
24
2
8
2
1
Pt(H L )Cl ] 4H O
.
[
C H Cl N O PtS
2
2
2
7
18
2 4 4
1
Ag(H L )(H O)NO ] 2H O 405.87
.
[
C H AgN O S
Grey
Buff
—
26.17
(26.58)
13.25
2
2
3
2
7
16
5 6
2
Zn(HL ) Cl ]
.
[
C H Cl N O S Zn
502.39
559.08
366.19
353.55
13.87
2
2
(33.44) (3.58) (16.72) (12.74) (14.13) (13.02)
1
4
18
2 6 2 2
2
Pt(L ) ]
[
Dark green 260–270
29.69
(30.05) (2.86) (15.02) (11.45)
23.10 5.04 11.65 8.38
(22.94) (4.92) (11.47) (8.74)
23.57 3.71 12.04 8.87
(23.76) (3.68) (11.88) (9.05)
2.92
15.31
11.34
—
35.33
(34.89)
16.33
20.8
7.7
2
C H N O PtS
2
1
4
16
6
2
2
Ni(L )(H O) Cl] 3H O
.
[
C H ClN NiO S
Green
228
9.52
(9.69)
20.21
2
2
2
(16.03)
17.62
7
18
3
6
2
Cu(HL )(H O)Cl ] H O
.
[
C H Cl CuN O S
Brownish
red
160–170
16.3
2
2
2
(20.08) (17.97)
7
13
2
3 3

3
94
N. S. YOUSSEF AND K. H. HEGAB
TABLE 2
Thermogravimetric analysis results of the investigated metal complexes of the ligands H L and HL
1
2
2
Water elimination
Hydrated water
mass loss %
Coordinated water
mass loss %
Residue (%)
Other
decomposition
stages (8C)
Temp.
(8C)
Found
(calcd.)
Temp.
(8C)
Found
(calcd.)
Temp.
(8C)
Found
(calcd.)
Complex
M:L
1:2
160–201
201–490
1
Cu(H L ) Cl ] 5H O
.
[
[
[
[
[
[
115
15.51
15.29)
—
—
—
—
—
—
607
13.61
(13.52)
Cu2S
2
2
2
2
(
(
(
4
1
90–607
80–240
1
Ni(H L )Cl ] H O
.
1:1
1:1
1:1
1:1
1:1
102
114
110
120
103
5.57
5.46)
240–350
758
518
707
760
718
22.92
(24.27)
Ni3S2
2
2
2
(
3
2
50–758
33–425
1
Pt(H L )Cl ] 4H O
.
13.58
13.84)
—
425–518
43.10
(43.66)
PtS
2
2
2
120–245
245–604
1
Ag(H L )(H O)NO ] 2H O
.
9.03
8.87)
—
27.01
(26.60)
Ag
2
2
3
2
(
6
2
04–707
15–250
2
Ni(L )(H O) Cl] 3H O
.
14.89
14.75)
150–215
10.07
(9.83)
250–536
21.43
(20.40)
NiO
2
2
2
5
1
36–760
13–200
2
Cu(HL )(H O)Cl ] H O
.
4.76
5.09)
—
—
200–434
23.39
(22.50)
CuO
2
2
2
(
4
34–718
2 21
coordination of the ligand HL through the furan oxygen atom by the band observed at 1320 cm due to a coordinated nitrate
(Jouad et al., 2001b). This is supported by the presence of the group (Bellamy, 1978). The coordination of the nitrate group
n(M–O) vibration (Jouad et al., 2001) at 428–435 cm
2
1
21
has been ascertained by the band at 321 cm , which may be
.
The presence of n(C 55 N), n(furan ring) and n(C–O–C) in reasonably assigned to n(M–O) of the O–NO group (Shakir
2
2
case of the [Zn(HL ) Cl ] complex at the same position as et al., 2003).
2
2
those in the uncomplexed ligand, together with the n(N–H)
shift to higher wave number and the absence of any band due
to M–O and M–N stretching vibrations, are consistent with
nondeprotonation and the sole coordination through the
1
H NMR Spectra
1
The H NMR spectra of the ligands H L and HL and their
1
2
2
sulfur atom (Castineiras et al., 2001).
The molar conductance of [Ag(H L )(H O)NO ] 2H O are collected in Table 4. The H NMR spectra of the
diamagnetic complexes in DMSO solutions with assignments
1
1
.
2
21
2
3
2
2
1
2
complex in DMF is 36.0 V cm mol , which indicates that free ligands showed exchangeable singlets assigned to the
1
the ligand H L is coordinated to the Ag(I) ion as non-deproto- imino proton and the amino protons at 10.03–10.38 and
2
nated chelating agent and that the nitrate ion is also coordinated 8.09–8.49 ppm, respectively. These signals disappeared in
to the silver ion (Ali et al., 1996), which may also be supported the presence of D O.
2

TABLE 3
2
IR frequencies of the bands (cm ) of H L and HL ligands and their complexes and their assignments
1
1
2
2
n(C 55 N)
n(C 55 S)
Compound
n(NH2) n(NH) þ n(C–C) n(ring) n(C–O–C) n(N–N) þ n(C–N) n(C 55 S) n(M–N) n(M–O) n(M–S) n(S–H)
3
480 m 3360 m
3420 m 3240 m
180 m
1640 m
1590 s
1520 s
830 s
750 s
1
Ligand H2L
1515 s
1520 w
1515 s
1035 s
1045 s
1050 s
1280 s
1260 m
1235 s
3
1
1
620 s
540 m
820 w
770 w
820 m
750 s
412 w
389 m
1
Cu(H L ) Cl ] 5H O
.
[
3400–3200 b
311 m
301 m
2
2
2
2
3480– 3360 m
3400 w 3240 m
1640 s
1600 m
1
Ni(H L )Cl ] H O
.
[
332 b
403 s
2
2
2
7
00 s
3540 w 3360 m
3440 b 3180 m
1600 s
1560 s
1305 s
1205 m
1170 s
770 s
730 s
1
Pd(H L ) ]Cl 2H O
.
[
[
[
1520 w
1520 s
1050 s
1040 s
300 m
300 m
300 s
2
2
2
2
1540 m
3440 b
3360 b
820 m
740 s
680 m
815 s
730 s
695 m
920 s
840 s
3
3
600–
560 b
1
Pt(H L )Cl ] 4H O
.
1600 m
1560 m
1310 w
1270 m
348 m
368 m
2
2
2
3280 b
360 b
3
Ag(H L )(H O)NO ] 2H O 3560 b 3280 w
1
.
1620 m
1570 s
1520 m
1020 s
1020 s
1045 s
1100 s
1090 w
—
321 w
2
2
3
2
3180 w
3
600 s 3380–
480 s 3140 m
2
Ligand HL
1590 s
1290 m
1285 b
1390 m
1370 w
3
3420 m
3500 b 3300 m
2
Zn(HL ) Cl ]
[
[
[
[
1590 s
820 w
930 s
—
—
344 s
2
2
3
220 w
360 m
3
2
Pt(L ) ]
3560 b 3220 w
100 b
1640 s
1600 s
1020 m
1000 m
1010 w
1300 s
1235 s
1190 s
1130 s
1150 m
1140 s
—
560 s
600 s
600 s
—
362 s
2
3
1640 s
1610 s
1570 w
1440 s
1390 s
1350 s
2
Ni(L )(H O) Cl] 3H O
.
3380 b 3260 m
790 s
700 s
435 m
428 m
408 m
2
2
2
3
080 m
370 m
3
2
Cu(HL )(H O)Cl ] H O
.
3480 b 3260 m
000 b
1630 s
1600 s
—
—
340 m 2120 s
2
2
2
3

3
96
N. S. YOUSSEF AND K. H. HEGAB
TABLE 4
H NMR spectral data of the ligands H L and HL and their diamagnetic Ni(II), Pd(II), Pt(II), Ag(I) and Zn(II) complexes
1
1
2
2
recorded in DMSO-d solution
6
1
H NMR signals (d, ppm) and their assignments
Ligands and their Complexes
Acetyl CH3
CS-NH2
CS-NH
N(1)H (Pyrrole)
1
Ligand H2L
2.50
8.26
10.03
11.30
8
.13
8.28
.19
8.64
.16
8.84
.82
8.49
.09
8.26
.05
7.71
.54
1
Ni(H L )Cl ] H O
.
[
[
[
2.58
2.35
2.54
2.52
2.52
2.58
9.83
10.50
10.68
10.38
10.12
—
11.39
10.95
11.47
2
2
2
8
1
Pd(H L ) ]Cl 2H O
.
2
2
2
2
8
1
Ag(H L )(H O)NO ] 2H O
.
2
2
3
2
8
2
Ligand HL
8
2
Zn(HL ) ]Cl
[
[
2
2
8
2
Pt(L ) ]
2
7
1
The absence of the imino proton signal in the spectra of the these complexes. The bands of the free ligands H L and HL
2
2
2
[
possible coordination of the Pt(II) ion to the thiol sulfur thioamide transitions within the thiosemicarbazone moiety.
Pt(L ) ] complex suggests deprotonation of the ligand and in the 300–340 nm range are attributable to the imine and
2
1
Kovala-Demertzi et al., 2000). The [Pt(H L )Cl ] 4H O
.
(
The
observed
.
magnetic
moment
of
the
complex is insufficiently soluble in DMSO-d to acquire a [Cu(H L ) ]Cl 5H O complex is 1.75 B.M. The electronic
2
2
2
1
6
2
2
2
2
1
H NMR spectrum. The signals due to the hydrazinic spectrum of this complex shows a shoulder at 500 nm assignable
2
2
protons are either shielded or deshielded in case of to the B ! E transition overlapped with the S(p) ! Cu(II)
1
g
g
1
Ni(H L )Cl ] H O,
1
[Pd(H L ) ]Cl 2H O,
1
.
.
[
[Ag(H L ) transition (Jasinski et al., 2003; Shakir et al., 1996) and a broad
2
2
2
2
2
2
2
2
2
.
(
non-deprotonation and coordination through sulfur atom in suggesting a square-planar geometry around the Cu(II) ion
H O)NO ] 2H O and [Zn(HL ) Cl ] complexes confirming band centered at 380 nm due to the S(s) ! Cu(II) transition,
2
3
2
2
2
2
(Jasinski et al., 2003). On the other hand, the [Cu(HL )(H O)
these complexes (Carballo et al., 2001).
1
2
1
.
The H NMR spectra of all H2L complexes and the Cl ] H O complex has a magnetic moment ¼ 1.85 B.M. and
2
2
2
[
Pt(L ) ] complex show that the acetyl methyl signal is either the electronic spectrum of this complex exhibits a broad band
2
2
2
shifted to higher or lower field on coordination, indicative centered at 580 nm assigned to the E ! T transition, indi-
g
2g
of variation in the electron density at the C 55 N group cating a distorted octahedral configuration (Ali et al., 2001).
Kovala-Demertzi et al., 2000). However, no shift of this The electronic spectrum of the diamagnetic
signal was observed in case of the [Zn(HL ) Cl ] spectra, con- [Ni(H L )Cl ] H O complex has a band at 450 nm due to a
(
2
1
.
2
2
2
2
2
1
1
firming that the azomethine N is not involved in coordination. combination of A ! B and S ! Ni(II) CT transitions
1
g
1g
1
1
The presence of two amino proton signals in the spectra of and bands at 530 and 600 nm attributable to the A ! A
1
g
2g
1
2
1
1
the H L and HL complexes shows magnetic non-equivalence and A ! E transitions, consistent with its planar stereo-
2
1g
g
attributable to rotation about the CS–NH bond being impeded chemistry (Fostiak et al., 2002). The magnetic moment of the
2
2
by partial double bond character acquired upon S-coordination [Ni(L )(H O) Cl] 3H O complex is 3.24 B.M., which is
.
2
2
2
(Castineiras et al., 2001). It may be also noted that coordination typical of high-spin octahedral complexes (Garcia et al.,
2
of the ligand HL in the deprotonated form leads to an upfield 2002). The electronic spectrum of this complex has absorption
2
3
3
shift in the NH2 signals in case of the [Pt(L ) ] spectra bands at 850 and 590–610 nm, assigned to the A ! T (P)
2
2g
1g
3
3
(
Loabana et al., 1998).
and A ! T (F) transitions, respectively, suggesting an
2
g
1g
octahedral geometry (Fostiak et al., 2002).
A presumably tetrahedral structure is suggested for the dia-
Electronic Spectra and Magnetic Susceptibility
Listed in Table 5 are the electronic transitions for H L and magnetic [Zn(HL ) Cl ] and [Ag(H L )(H O)NO ] 2H O
2
HL and their metal complexes with the magnetic moments of complexes (Wu et al., 1999).
1
2
1
.
2
2
2
2
2
3
2

SYNTHESIS AND CHARACTERIZATION OF SOME TRANSITION METAL COMPLEXES
397
TABLE 5
Electronic absorption spectral bands of the ligands H L and HL and their complexes
1
2
2
Electronic absorption bands lmax (nm)
Ligands
and their complexes
Intraligand & charge
tranfer bands
Mode
d–d bands
meff. (B.M.)
1
Ligand H2L
Nujol
DMSO
Nujol
DMSO
Nujol
DMSO
Nujol
DMSO
Nujol
DMF
260, 300, 310, 330, 340
254 (4.10), 328 (4.22)
240, 290, 320, 380
1
Cu(H L ) Cl ] 5H O
.
[
[
[
[
[
2
2
2
2
500 sh
1.75
250 (4.18), 290 (4.23), 330 (4.32)
240, 275, 340, 360, 385, 450
330 (4.42)
1
Ni(H L )Cl ] H O
.
530, 600
Diamagnetic
2
2
2
1
Pd(H L ) ]Cl 2H O
.
230, 260, 325
280 (4.18), 310 (4.33)
310, 320, 350, 390
470
Diamagnetic
Diamagnetic
Diamagnetic
2
2
2
2
418 (2.38), 590 sh (2.08)
520
455 (2.79), 590 sh
1
Pt(H L )Cl ] 4H O
.
2
2
2
255 (4.15), 335 (4.31)
220, 360, 380
1
Ag(H L )(H O)NO ] 2H O
.
Nujol
DMSO
Nujol
DMF
2
2
3
2
260 (4.25), 330 (4.37), 430 sh
262, 322
2
Ligand HL
210 (3.91), 249 (3.74), 314 (3.65)
255, 245, 290, 320, 355, 385
258 (3.98), 320 (3.85), 360 sh
255, 245, 330, 380
2
Zn(HL ) ]Cl
[
[
Nujol
DMF
Diamagnetic
Diamagnetic
2
2
2
Pt(L ) ]
Nujol
DMF
450, 510
595 (2.54)
2
209 (3.95), 248 (3.90),
316 (4.11), 363 sh
2
Ni(L )(H O) Cl] 3H O
.
[
[
Nujol
DMF
245, 330, 390, 450 sh
270 (4.13)
510 sh
590 sh (1.90), 610(1.27),
3.24
1.85
2
2
2
850 sh
495 sh
580 (2.37)
2
Cu(HL )(H O)Cl ] H O
.
Nujol
DMF
250, 310, 320, 330, 380
270 (4.02), 330 (3.96)
2
2
2
2
Numbers in parantheses log e (e, lit. mol. cm ).
1
21
2
The electronic spectra of the Pd and Pt complexes are [Cu(HL )(H O)Cl ] H O complexes have four decomposition
.
2
2
2
indicative of square-planar geometry. The absorption bands steps. These complexes show the first mass loss step, attributed
of these complexes at 418–455, 470–520 and 590–595 nm to dehydration, in the temperature range 102 to 1208C. The
1
1
may be assigned to the one-electron transitions A ! E , second decomposition step of these complexes starts around
1
g
g
1
1
1
1
1
.
A1g ! B and A ! A , respectively (Kovala-Demertzi 113–1808C. In case of [Ag(H L )(H O)NO ] 2H O and
1g
1g
2g
2
2
3
2
2
.
[Cu(HL )(H O)Cl ] H O complexes, abrupt mass losses
2 2 2
et al., 2001).
occur at 120–245 and at 113–2008C, respectively, which
may represent the removal of coordinated water associated
Thermogravimetric Analyses
The thermogravimetric data for the studied complexes are with the other products of the second decomposition step.
listed in Table 2. The results obtained are in good agreement The third and the fourth decomposition steps are in the range
with the theoretical formulae suggested from the elemental of 201–604 and 434–7608C, respectively. The fourth step
analyses.
ends with the formation of silver metal in case of the silver
The first mass loss from all H L and HL complexes in the complex or the corresponding sulfides, Cu S and Ni S in
1
2
2
2
3
.
2
1
1
.
temperature range of 102–1208C, may be due to the loss of case of [Cu(H L ) ]Cl 5H O and [Ni(H L )Cl ] H O,
2
2
2
2
2
2
2
1
hydrated water in these complexes. The mass loss in the temp- respectively. In case of the [Pt(H L )Cl ] 4H O complex,
.
2
2
2
2
.
erature range of 150–2158C from the [Ni(L )(H O) Cl] 3H O there are three decomposition steps. The first mass loss step
2
2
2
complex indicates the elimination of coordinated water starts at 1148C, which could be due to the removal of lattice
molecules.
water. The second step starts at 2338C, whereas the third one
1
1
.
.
The [Cu(H L ) ]Cl 5H O, [Ag(H L )(H O)NO ] 2H O, is in the range 425–5188C and comprises the formation of
2
.
2
2
2
2
2
.
3
2
1
Ni(H L )Cl ] H O,
2
[Ni(L )(H O) Cl] 3H O
[
and PtS, followed by decomposition into Pt.
2
2
2
2
2
2

3
98
N. S. YOUSSEF AND K. H. HEGAB
2
In the case of [Ni(L )(H O) Cl] 3H O and [Cu(HL )
2
.
2
2
2
.
(H O)Cl ] H O complexes, the fourth step ends with the for-
2 2 2
mation of the corresponding oxides: NiO and CuO,
respectively.
The amounts of residue are in good agreement with the cal-
culated values.
Suggested Structural Formulae of the Complexes
From the spectral data and the elemental and thermal
analyses, the structure of the prepared complexes may be for-
mulated as shown in Figures 2 and 3.
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