Synthesis, characterization, and spectral and thermal studies of some divalent transition metal complexes of benzylpiperazine dithiocarbamate

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SYNTHESIS, CHARACTERIZATION, AND SPECTRAL
AND THERMAL STUDIES OF SOME DIVALENT
TRANSITION METAL COMPLEXES OF BENZYLPIPERAZINE
DITHIOCARBAMATE
Hasan Cesur a , Turan K. Yazicilar a , Bekir Bati a & Veysel T. Yilmaz b
a Department of Chemistry, Faculty of Arts and Sciences , Ondokuz Mayis University , 55139,
Kurupelit, Samsun, Turkey
b Department of Chemistry, Faculty of Arts and Sciences , Ondokuz Mayis University , 55139,
Kurupelit, Samsun, Turkey
Published online: 15 Feb 2007.
To cite this article: Hasan Cesur , Turan K. Yazicilar , Bekir Bati & Veysel T. Yilmaz (2001) SYNTHESIS, CHARACTERIZATION,
AND SPECTRAL AND THERMAL STUDIES OF SOME DIVALENT TRANSITION METAL COMPLEXES OF BENZYLPIPERAZINE
DITHIOCARBAMATE, Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry, 31:7, 1271-1283, DOI: 10.1081/
SIM-100106863
To link to this article: http://dx.doi.org/10.1081/SIM-100106863
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SYNTH. REACT. INORG. MET.-ORG. CHEM., 31(7), 1271–1283 (2001)
SYNTHESIS, CHARACTERIZATION, AND
SPECTRAL AND THERMAL STUDIES OF
SOME DIVALENT TRANSITION METAL
COMPLEXES OF BENZYLPIPERAZINE
DITHIOCARBAMATE
Hasan Cesur, Turan K. Yazlcllar, Bekir Bati,
and VeyselT. Y llmaz*
Department of Chemistry, Faculty of Arts and Sciences,
Ondokuz Mayis University, 55139 Kurupelit,
Samsun, Turkey
ABSTRACT
Potassium benzylpiperazine dithiocarbamate (KBPDTC) and
its complexes with Mn(II), Co(II), Ni(II), Cu(II) and Zn(II)
have been synthesized and characterized. On the basis of
elemental analyses, magnetic moments and spectral data, the
monoanionic BPDTC ligand coordinates to the metal ions via
both sulfur atoms of the -NCS2 group, acting as a bidentate
ligand. The Ni(II) complex has a square-planar coordination
geometry, while the other complexes are suggested to exhibit a
*Corresponding author. E-mail: vtyilmaz@omu.edu.tr
1271
Copyright # 2001by Marcel Dekker, Inc.
www.dekker.com

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CESUR ET AL.
square-pyramidal coordination environment. The thermal
reactivity of KBPDTC.H2O and its metal complexes has been
studied by means of DTA and TG techniques. Thermo-
analytical data show that decomposition of the metal com-
plexes of KBPDTC under nitrogen gives the corresponding
metal thiocyanates as stable solid intermediates.
INTRODUCTION
The complexing ability of dithiocarbamates (DTC) with metals has
been known for many years. DTC forms a chelate with virtually all tran-
sition metal ions through its two-donor sulfur atoms1. Furthermore, the
bidentate anion also acts as a bridge between two transition metal centers2.
DTCs were used for analytical applications, especially for the separation
and determination of metals as metal chelates in thin-layer3, liquid4 and gas
chromatography5. Some salts of DTC derivatives exhibit interesting biolo-
gical effects including anti-alkylation6;7, anti-HIV properties8 and antitumor
activity against leucemic cells9. They are also used as cadmium antidote10.
Large quantities of water-soluble DTC complexes are used in agriculture
as fungicides or pesticides11 and also were tested in various medical
applications12.
In recent years, the study of transition metal complexes of sub-
stituted DTC complexes has been a subject of considerable interest
because of their structural, magnetic, electrochemical and thermal pro-
perties13ꢀ22. Piperazine dithiocarbamate and its Zn(II) complex were
previously synthesized and used for determination of some transition
metals23. In this paper, we report the synthesis, characterization, spectral
and thermal properties of the potassium salt of benzylpiperazine dithio-
carbamate (KBPDTC.H2O) ligand (Fig. 1) and its Mn(II), Co(II), Ni(II),
Cu(II) and Zn(II) complexes.
Figure 1. Structural formula of the ligand (KBPDTC).

DITHIOCARBAMATE COMPLEXES
EXPERIMENTAL
Reagents and Instruments
1273
1-Benzylpiperazine was purchased from Aldrich, while CS2 and metal
salts were from Merck. All other reagents were of the purest available grade.
Electronic spectra were measured using a Unicam UV2 spectrophotometer
in chloroform in the 2007800 nm range. IR spectra were recorded on a
Mattson FTIR spectrophotometer as KBr pellets. Room temperature
magnetic susceptibility measurements were carried out on a Sherwood
Scientific MXI model Gouy magnetic balance. C, H and N analyses were
carried out at the TUBITAK Marmara Research Centre (Gebze). The
simultaneous TG, DTG and DTA curves were obtained using a Rigaku
TG8110 thermal analyser combined with a TAS100 thermogravimetric
analyser. The experiments were carried out in a dynamic nitrogen atmo-
sphere with a flow rate of 80 mL minꢀ1 in the temperature range
2071000 ꢁC, usingꢁ platinum crucibles. Sample sizes of 5710 mg and a
heating rate of 10 C minꢀ1 were used. Sintered a-alumina was used as the
reference material.
Synthesis of Potassium Benzylpiperazine Dithiocarbamate
KOH (5.6 g, 0.1mol) dissolved in 100 mL H O was mixed with a
2
diethyl ether solution (100 mL) containing benzylpiperazine (17.6 g,
0.1mol). CS 2 (7.6 g, 0.1mol) was added dropwise to this solution in a water-
ice bath at about 0 ꢁC. The resulting solution was stirred for 60 min at 0 ꢁC
and then transferred into a separatory funnel. The aqueous phase was
separated and then evaporated in a water bath at 95 ꢁC. The solid potassium
benzylpiperazine dithiocarbamate (KBPDTC) obtained was washed with
diethyl ether for several times and dried in air.
Synthesis of MetalCompelxes of KBPDTC
The metal nitrates (0.005 mol) dissolved in distilled H2O (50 mL) were
added with stirring to a solution of KBPDTC (3.08 g, 0.01mol) in H 2O
(50 mL). The metal complexes precipitated immediately as polycrystalline
solids and were filtered by suction, washed with H2O, diethyl ether, and
dried in air.

1274
CESUR ET AL.
RESULTS AND DISCUSSION
Synthesis
The KBPDTC complexes of the formula [M2(BPDTC)4] (M ¼ Mn(II),
Co(II), Ni(II), Cu(II) or Zn(II)) have been prepared by the reaction of the
metal salts with the ligand KBPDTC.H2O. Analytical data and some phy-
sico-chemical properties of the isolated solid metal complexes are given in
Table I. The structures proposed for the metal complexes are in accordance
with elemental analysis data. These complexes are air-stable and were
obtained in high yield. They are insoluble in water, but sparingly soluble in
ethanol, acetone, chloroform and CCl4. As will be discussed later, thermal
analysis data show that the ligand and its Mn(II), Co(II) and Zn(II) com-
plexes contain lattice water molecules. All the complexes melt at the tem-
peratures given in Table I with the melting points appearing as sharp and
narrow peaks in the DTA curves.
4KBPDTC þ 2MðNO3Þ2 ꢀ! ½ M2ðBPDTCÞ4Š þ 4KNO3
SpectralCharacteristics
Electronic spectra of KBPDTCÁH2O show two strong absorption
bands at 246 and 285 nm in the UV region (Table II). These bands are
due to n ! pà and p ! pà transitions. In all the metal complexes, bands
below 300 nm are attributed to intra-ligand transitions. The intense bands
at 326, 392 and 436 nm in the spectra of the Co(II), Ni(II) and Cu(II)
complexes, respectively, are ascribed to charge transfer processes18, pro-
bably from ligand to metal, mainly associated with the N-C¼S and
S-C¼S groups. The absorptions at higher wave lengths are due to d-d
transitions24.
Table II also summarizes the most significant frequencies in the IR
spectral data of the potassium salt of the ligand and the corresponding metal
complexes. The n(CS) asymmetric stretching bands are located prominently
in the range 99071030 cmꢀ1 in the potassium salt of the ligand and all the
metal complexes as a doublet, while the symmetric n(CS) bands appear at
approximately 690 cmꢀ1 as weak absorptions25. These bands are considered
indicative of DTC acting as a bidentate ligand16. The absorption of the
NCS2 group occurs at around 1100 cmꢀ1 and shifts to higher frequency
by about 45 cmꢀ1 in the metal complexes. The bands in the range
141071525 cmꢀ1 are attributed to the n(CN) stretching vibration of the
thioureide group in the potassium salt of the ligand, and also shifted higher

DITHIOCARBAMATE COMPLEXES
1275

1276
CESUR ET AL.

DITHIOCARBAMATE COMPLEXES
1277
in the spectra of the metal complexes. The same observations were reported
for amino acid DTCs18, and DTC complexes with piperidine or pyr-
rolidine19. The stretching vibrations of the M-S bonds appear at
3007500 cmꢀ1 as weak bands26.
Magnetic moment measurements showed that the Ni(II) complex is
diamagnetic, while the Mn(II), Co(II), and Cu(II) complexes are para-
magnetic (Table I). The room temperature magnetic moment values are
consistent with a square-planar coordination for the Ni(II) complex and a
square-pyramidal coordination for the Mn(II), Co(II), and Cu(II) com-
plexes. The Zn(II) complex was found to be diamagnetic as expected.
ThermalDecomposition Behaviour
The thermal behaviour of the ligand and all of the complexes has been
followed up to 1000 ꢁC. Thermoanalytical data (mass losses, temperature
ranges, peak temperatures and solid decomposition residues) of the ligand
and its metal complexes are given in Table III. KBPDTC.H2O decomposes
in two steps. The first step between 32 and 90 ꢁC corresponds to dehydra-
tion. After dehydration, it melts at 215 ꢁC and then begins to decompose
ꢁ
with melting at ca. 21 6 C. Degradation of the organic part of the ligand
takes place in the second decomposition stage in the range 2167400 ꢁC, with
three endothermic maxima. The final decomposition product was identified
by IR spectra and mass loss calculations as KSCN.
The Mn(II) complex loses its lattice water at 64 ꢁC and is thermally
stable up to the melting point at 146 ꢁC. Endothermic decomposition of the
BPDTC moiety occurs in the temperature range 1497357 ꢁC as a multistep
process. Mass loss calculations correspond to formation of Mn(SCN)2 (total
mass loss, found: 70.76%; calcd.: 69.32%). The Co(II) complex shows initial
loss of water in the 25798 ꢁC range, corresponding to two molecules of
water (mass loss, found 5.73%; calcd. 6.02%). The decomposition process
begins with melting at 235 ꢁC and continues to produce cobalt thiocyanate
at ca. 330 ꢁC. The anhydrous Ni(II) complex exhibits a single-stage
decomposition. The endothermic degradation of the BPDTC moiety takes
place in the temperature range 2877400 ꢁC with two maxima, after melting
at 282 ꢁC. Ni(SCN)2 was found to be the solid decomposition product at
about 400 ꢁC. The thermal analysis curves of the Cu(II) complex also sug-
gest a two-stage degradation process in the 2387341 ꢁC range, caused by
decomposition of BPDTC to form the respective thiocyanate. The Zn(II)
complex loses its lattice water at 44 ꢁC and begins to decompose after
melting at 217 ꢁC. Decomposition of the complex is followed by evaporation
of the decomposition intermediates, leaving an empty crucible at about

1278
CESUR ET AL.

DITHIOCARBAMATE COMPLEXES
1279
370 ꢁC. The volatile behaviour of the Zn(II) and Cd(II) complexes
with diisobutyldithiocarbamate was reported by Glinskaya and
co-workers14;27;28
.
The present thermoanalytical data showed that under nitrogen, the
decomposition of the metal complexes of BPDTC gives the corresponding
metal thiocyanates as stable intermediates. IR spectroscopy was used for the
identification of the metal thiocyanates by the n(SCN) vibration frequency
around 2045 cmꢀ1. The decompositions of the thiocyanates proceed at a
slow rate at higher temperatures. The literature suggests that metal thio-
cyanates are common products in the thermal decomposition of DTCs29,
although this conclusion does not apply as a general rule to some cyclic
DTCs18;19. It was suggested that the thermal decomposition behaviour of
the metal complexes of DTCs is related to the coordination of the DTC
ligand to the metal ion. The monodentate complexes decompose in a single
stage, while the bidentate complexes show two decomposition steps to give
the corresponding metal thiocyanates19. The observations reported in this
paper are in agreement with the earlier explanations.
Structures of MetalCompelxes
All the complexes, except the Ni(II) complex, are dimeric with a metal
to ligand ratio of 1:2. It is not easy to decide from the IR spectra whether the
anionic BPDTC acts in a chelate or bridging mode. Attempts to prepare
suitable crystals for single crystal X-ray analysis were unsuccessful. The
diamagnetic behaviour of the Ni(II) complex clearly indicates that the Ni(II)
ion has a square-planar coordination geometry with the two bidentate
chelate sulfur atoms from two monoanionic BPDTC ligands to form a
monomeric structure. In the literature, only a few plain metal complexes of
DTCs have been crystallographically characterized14;16;17;30. From the
available data it is obvious that in these complexes, the molar ratio of
M:DTC is 1:2 and the complexes usually exhibit octahedral or square-
pyramidal coordination geometries as illustrated in Fig. 2. The octahedral
coordination results in the formation of a polymeric structure (A), while the
square-pyramidal coordination gives a dimeric structure (B). In both
structures, the MS4 unit is square-planar and one of the sulfur atoms acts as
a bridge to occupy the axial or the apical positions. Thus, the DTC ligands
perform a bridging cyclic tridentate function. In the mixed-ligand complexes
of DTCs, the donor atoms of the co-ligands occupy the axial positions to
form octahedral complexes27;28;31. On the basis of the observed elemental
analyses and magnetic moments, it may be suggested that the structure of
the plain KBPDTC complexes with Mn(II), Co(II), Cu(II) and Zn(II) is

1280
CESUR ET AL.
Figure 2. The structures of the BPDTC complexes.
square-pyramidal and adopts the dimeric structure (B). The experimental
magnetic moment (3.71B.M.) of the Mn(II) complex supports the proposed
assignment and, furthermore, the solubility of the BPDTC complexes in
ethanol, acetone, chloroform and CCl4 may be also indicative for the
dimeric composition, since polymeric complexes will not be soluble.
ACKNOWLEDGMENT
This work was supported by the Research Fund of Ondokuz Mayis
University, Samsun, Turkey.
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Received February 7, 2001
Accepted June 7, 2001
Referee I: N. V. Duffy
Referee II: T. R. Webb