Synthesis and investigation of mixed-ligand transition metal complexes of alkyl dithiocarbonate and benzoylhydrazine or benzoylhydrazone derivatives

Article abstract of DOI:10.1081/SIM-120035954

Mixed-ligand complexes of the types [Ni(Etdtcn)(BH)], [Ni(Budtcn) (BeBH)], and [M(Rdtcn)(salBH)], where M = Co(II), Ni(II), or Cu(II); R = methyl (Me), ethyl (Et), propyl (Prop) or butyl of the dithiocarbonate (Bu); dtcn = dithiocarbonate group; BH = benzoyl-hydrazine anion, BeBH = benzaldehyde benzoylhydrazone anion, and salBH = salicylaldehyde benzoylhydrazone anion have been synthesised. Elemental analyses, molar conductivities, and spectral (IR, UV, and mass) studies have been used to elucidate the structure of the metal complexes. HBH and HBeBH coordinate in the enol form as bidentate ligands forming a square-planar structure around Ni(II). Moreover, the HsalBH ligand behaves as tridentate anion with all metal ions and an octahedral structure for these complexes is proposed. The three ligands and some of their complexes were screened against three species of bacteria, namely B. cereus (G + ve), P. aeruginosa (G - ve), and S. aureus (G + ve) and five types of fungi, A. flavus, A. fumigatus var. albus, A. niger, F. oxysporum or C. tropicum. The HsalBH ligand has shown high activity against bacteria and fungi, probably due to the presence of a hydroxyl group in this ligand.

Full text of DOI:10.1081/SIM-120035954

SYNTHESIS AND REACTIVITY IN INORGANIC AND METAL-ORGANIC CHEMISTRY
Vol. 34, No. 4, pp. 743–762, 2004
Synthesis and Investigation of Mixed-
Ligand Transition Metal Complexes of Alkyl
Dithiocarbonate and Benzoylhydrazine
or Benzoylhydrazone Derivatives
*
Amna S. A. Zidan
Department of Chemistry, Faculty of Science, Assiut University,
Assiut, Egypt
ABSTRACT
Mixed-ligand complexes of the types [Ni(Etdtcn)(BH)], [Ni(Budtcn)
(BeBH)], and [M(Rdtcn)(salBH)], where M ¼ Co(II), Ni(II), or Cu(II);
R ¼ methyl (Me), ethyl (Et), propyl (Prop) or butyl of the dithiocarbonate
(Bu); dtcn ¼ dithiocarbonate group; BH ¼ benzoyl-hydrazine anion,
BeBH ¼ benzaldehyde benzoylhydrazone anion, and salBH ¼ salicyl-
aldehyde benzoylhydrazone anion have been synthesised. Elemental
analyses, molar conductivities, and spectral (IR, UV, and mass) studies
have been used to elucidate the structure of the metal complexes. HBH
and HBeBH coordinate in the enol form as bidentate ligands forming a
square-planar structure around Ni(II). Moreover, the HsalBH ligand
*
Correspondence: Amna S. A. Zidan, Department of Chemistry, Faculty of Science,
Assiut University, Assiut, 71516, Egypt; E-mail: amna@aun.edu.eg.
743
DOI: 10.1081/SIM-120035954
0094-5714 (Print); 1532-2440 (Online)
www.dekker.com
Copyright # 2004 by Marcel Dekker, Inc.

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behaves as tridentate anion with all metal ions and an octahedral structure
for these complexes is proposed. The three ligands and some of their com-
plexes were screened against three species of bacteria, namely B. cereus
(G þve), P. aeruginosa (G 2ve), and S. aureus (G þve) and five types
of fungi, A. flavus, A. fumigatus var. albus, A. niger, F. oxysporum or
C. tropicum. The HsalBH ligand has shown high activity against bacteria
and fungi, probably due to the presence of a hydroxyl group in this ligand.
Key Words: Mixed-ligand complexes; Spectral studies; TG-DTG;
Thermogravimetry.
INTRODUCTION
The interest in the study of hydrazones has been growing due to their use in
biological systems and analytical chemistry.[1,2] Interest in such studies also has
arisen mainly due to structural problems[3] and the tendency of hydrazides to
function as antituberculous, antifungal, and antiviral agents in view of their abil-
ity to form metal chelates.[4,5] Further, hydrazones can coordinate to transition
metals either in the enolic form (I) or in the keto form (II) as shown in Fig. 1.[6,7]
As a part of our program on the synthesis of several ternary complexes,[8–10]
the present investigation is concerned with a systematic study of ternary
complexes of divalent metal ions with the biological active benzoylhydrazine
(HBH), benzaldehyde benzoylhydrazone (HBeBH), or salicylaldehyde
benozylhydrazone (HsalBH) and alkyl dithiocarbonate (Fig. 2).
EXPERIMENTAL
All chemicals were of analytical grade. Benzoylhydrazine,[11] benzal-
dehyde benzoylhydrazone, salicylaldehyde benozylhydrazone,[7] and potassium
alkyl dithiocarbonate[12] were prepared according to literature procedures.
Figure 1. Structures of enol (I) and keto (II) forms of hydrazone complexes.

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Figure 2. Structures of the ligands.
Synthesis of the Complexes
A quantity of 0.1 mmol of benzoylhydrazine (HBH), benzaldehyde benz-
oylhydrazone (HBeBH), or salicylaldehyde benzoylhydrazone (HsalBH) was
dissolved in 20 mL absolute ethanol and added to 0.1 mmol of the respective
metal chloride in 10 mL of aqueous ethanol (70% EtOH). The mixture was
stirred for about 0.5 hr and then 0.1 mmol of potassium alkyldithiocarbonate
in 10 mL doubly distilled water was added to the mixture with continuous
stirring. A precipitate of the ternary complexes separated out, which was
filtered, washed with aqueous ethanol (80% ethanol), and dried over P2O5.
Physical Measurements
The elemental analysis data were recorded by an Analytischer Funktions-
test Vario El Fab-Nr. 11982027 elemental analyser. The infrared spectra were
obtained in the solid state (KBr) on a 470 Shimadzu infrared spectrophotometer.
Electronic spectra were recorded in DMF as solvent on a Shimadzu UV-2101
PC spectrophotometer. Thermogravimetric analyses were determined using

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an electrobalance of the type Sartorius 200 MP converted to a thermobalance by
addition of a small furnace and sample holder. The temperature was measured
using a chromal alumal thermocouple attached to a Soar type ME 550 digital
multimeter. The heating rate was adjusted to be 88C min21. Conductance
measurements were carried out using a LF Digi. 550 conductance meter. The
mass spectra were recorded on a Jeol JMS600 mass spectrophotometer.
RESULTS AND DISCUSSION
The analytical data of the complexes (Table 1) indicate that the ternary
complexes with metal ions formed according to the following equations:
NiCl2 þ HBH þ KEtdtcn ꢀ! ½NiðEtdtcnÞðBHÞꢁ þ KCl þ HCl
NiCl2 þ HBeBH þ KBudtcn ꢀ! ½NiðBudtcnÞðBeBHÞꢁ þ KCl þ HCl ð2Þ
MCl2 þ HsalBH þ KRdtcn ꢀ! ½MðRdtcnÞðsalBHÞꢁ þ KCl þ HCl ð3Þ
ð1Þ
where M ¼ Co(II), Ni(II), or Cu(II); R ¼ Me, Et, Prop, or Bu of the dithiocarbo-
nato anion; BH ¼ benzoylhydrazine anion; BeBH ¼ benzaldehyde benzoyl-
hydrazone anion; and salBH ¼ salicylaldhyde benzoylhydrazone anion.
The resulting complexes are coloured solids and have high melting points.
All complexes are soluble in DMF and DMSO and are partially soluble in
common organic solvents. The molar conductance of 1023 M solutions of
the compounds in anhydrous DMF lies in the range 7–10 ohm21 cm2 mol21
indicating their behaviour as non-electrolytes.
Attempted preparations of mixed-ligand complexes from the reaction of
cobalt(II) chloride or copper(II) chloride with benzoylhydrazine or benzalde-
hyde benzoylhydrazone and potassium alkyl dithiocarbonate were unsuccess-
ful, where the binary complexes of Co(II) or Cu(II) alkyl dithiocarbonates
precipitated. The analytical results of the prepared solids, along with their
colours and melting points are listed in Table 1.
IR Spectra
A comparison of the IR spectra (Table 2) of the ligands and their ternary
complexes shows the following:
1. The IR spectra of the two ligands HBH and HBeBH are similar,
except in the spectrum of HBH where there are two bands at 3400
and 3350 cm21 assigned to nas(NH2) and ns(NH2), respectively.
Moreover, bands at 3300–3280, 1665–1640, 1610–1590, and

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749

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880–980 cm21 were observed in the two ligands and are attributed to
n(NH), n(C55O), n(C55N), and n(N–N), respectively. These facts
suggest that the two ligands remained in the keto form in the solid
state (Fig. 2). Bonding of HBH and HBeBH to nickel(II) has been
suggested by a careful comparison of the infrared spectra of the com-
plexes with those of the free ligands. A few significant bands have
been selected to observe the effect of complexation on the ligand
vibration in the complexes. The two ligands in the complexes (1)
and (2) chelate with the Ni(II) ion in the enol form. This chelation
was supported by the following.
The shift to low frequency of the C55N (ꢀ10cm21) band and the
shift to higher frequency of the n(N–N) band and its splitting indicated
involvement of azomethine nitrogen in coordination.[13] Thus, both the
hydrazine and hydrazone behave as bidentate ligands. The first (HBH)
bonds through a –NH2 group and C–O in the enol form, and the second
ligand (HBeBH) bonds through the azomethine group and C–O in the
enol form[14] (Fig. 3). The two complexes showed the absence of C55O
and a shift to lower frequency of the –NH band in complex (1) and the
latter band disappeared in complex (2) with the appearance of new
bands at 1280 and 1285cm21, respectively, assigned to n(C–O),
suggesting enolization of the ligands on complexation,[15] and signifies
bonding of the terminal-NH2 group in complex (1).
2. A comparison of IR spectra of HsalBH and its metal complexes
shows the following.
(i) Two bands are appearing in the spectrum of the ligand at 3430
and 910 cm21, which were attributed to n(OH) and d(OH), respect-
ively. In the spectra of the complexes (3)–(14), d(OH) is absent
while it is difficult to trace the disappearance of n(OH) because it
occurs at the same range where n(NH) is located. This indicates the
deprotonation of the hydroxyl group and coordination of the ligand
as a mononegative anion. (ii) The band due to n(NH) remains unal-
tered compared to the ligand indicating non-participation of –NH
in coordination and also that the ligand coordinates in the keto
form. (iii) The shift to lower frequency of the two bands n(C55O)
and n(C55N) by 40–60 and 25–45 cm21, respectively, may suggest
bonding through the carbonyl oxygen and azomethine nitrogen.[16]
Coordination of nitrogen to the metal atom would be expected to
reduce the electron density in the azomethine links and thus cause a
shift in the n(C55N) band.[17] (iv) The small shift to higher
frequency of the n(N–N) band at ꢀ1025 cm21 and its splitting can
be taken as additional evidence for the participation of the
azomethine nitrogen in bonding.[13,18]

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751
Figure 3. Suggested structures for the complexes.
In conclusion, the HsalBH ligand acts with all metal ions as a
mononegative tridentate ligand coordinating via the oxygen of the
hydroxyl group, azomethine nitrogen, and carbonyl group in the keto
form (Fig. 3).
Moreover, all complexes (1)–(14) show some bands in the infrared spec-
tra due to the dithiocarbonate moiety and their assignments are as follows:
n(C–O–C), n(C–O) and n(C–S) are located in the regions 1090–1120,
1130–1150, and 1020–1030 cm21, respectively. The presence of only one
band at ꢀ1025 cm21 due to n(C–S) indicates the bidentate nature of the alkyl-
dithiocarbonate ligands in these complexes.[8–10] Further support for the
coordination of the two ligands to the metal ions was provided by the appear-
ance of bands at 520–560, 430–460, and 480–510 cm21, which are assigned
to n(M–O),[19] n(M–N),[19] and n(M–S),[9] respectively.

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Electronic Spectra
The electronic spectral data of the complexes under investigation are listed
in Table 3. The spectra of the complexes [Ni(Etdtcn)(BH)] and [Ni(Budtcn)
(BeBH)] in DMF show two bands in the region 15,120–15,981 and 20,408–
1
1
20,964 cm21 assignable to 1A1g ! A2g and 1A1g ! B1g transitions, respect-
ively, supporting a square-planar geometry around the Ni(II) ions.[20]
The electronic spectra of [Ni(Rdtcn)(salBH)] show three d–d transition
bands at 11,185–12,106, 15,060–16,420, and 24,096–24,331cm21. An exam-
ination of these bands reveals that these complexes have an octahedral geometry
3
3
and are assigned to the transitions 3A2g(F) ! T2g(F), 3A2g(F) ! T1g(F), and
3A2g ! T2g(P), respectively.[20–22] Complexes of the type [Co(Rdtcn)
3
(salBH)] display absorption bands in the two regions 15,974–16,129 and
20,790–21,142cm21. The positions of the bands indicate that these complexes
have an octahedral configuration.[20–22] The assignment of the spectral bands
4
4
4
4
may be given as T1g(F) ! A2g(F) (n2) and T1g(F) ! T1g(P) (n3),
respectively.
The electronic spectra of the Cu(II) complexes show three characteristic
bands in the d–d transition region, namely at 11,669–12,346, 17,123–17,530,
and 25,445–25,907 cm21. These bands have been assigned to the transitions
2
2
2
2
2
2B1g ! A1g, B1g ! B2g, and B1g ! Eg, respectively. On the basis of
which a distorted octahedral structure around the Cu(II) is proposed. The
broadening of the bands may be attributed to the Jahn–Teller effect.[23,24]
For all complexes (1)–(14), on the basis of the position and intensity, the
two bands at 23,683–33,580 and 38,769–48,077 cm21 are ascribed to charge
transfer and intraligand transitions, respectively.
Based on the above spectral studies, the structures in Fig. 3 are suggested
for the complexes.
Thermal Analysis
A thermogravimetric analysis of the complexes was made over the tem-
perature range 50–550 8C. The TG and DTG curves of the complex
[Ni(Etdtcn)(BH)] (Fig. 4) show three main steps and a number of DTG
peaks. The first step occurs at 125 8C corresponding to loss of a C2H4 molecule
from the ethyl dithiocarbonate group as shown by Eq. (4).
½NiðEtdtcnÞðBHÞꢁ ꢀ! ½NiðHOCS2ÞðBHÞꢁ þ CH255CH2
ð4Þ
Elimination of alkenes from alkyl dithiocarbonate was also observed
in the literature.[25] The second step contains three DTG peaks at 235,

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Table 3. Electronic spectral bands for the complexes in nmax cm21 (1 dm3 mol21 cm21).
Charge transfer
transition
Intraligand transfer
transition
No.
d–d Transition
(1)
15,120 (28); 20,408 (100)
24,390 (223)
43,290 (2,670);
46,083 (3,300);
47,847 (3,820)
(2)
15,981 (13); 20,964 (100)
23,683 (280)
44,643 (1,100);
46,512 (1,130);
48,077 (2,270)
(3)
(4)
(5)
(6)
11,919 (52); 15,985 (52);
24,213 (90)
30,769 (1,590)
30,769 (1,385)
30,769 (1,060)
30,864 (1,017)
40,486 (2,068)
38,769 (2,001)
40,847 (4,083)
39,370 (3,088)
11,820 (52); 16,420 (74);
24,213 (100)
11,185 (17); 15,060 (70);
24,096 (95)
12,106 (21); 16,097 (85);
24,331 (105)
(7)
(8)
15,974 (165); 20,790 (180)
16,077 (170); 20,790 (195)
16,129 (549); 21,142 (590)
16,103 (532); 21,053 (621)
33,003 (4,716)
33,113 (2,675)
29,155 (1,476)
33,110 (1,580)
30,395 (4,729)
43,290 (4,277)
40,841 (5,000)
39,364 (4,716)
40,041 (5,000)
42,735 (5,100)
(9)
(10)
(11)
11,669 (67); 17,123 (67);
25,907 (124)
(12)
(13)
(14)
12,346 (67); 17,241 (78);
25,445 (153)
33,112 (4,612)
32,820 (4,720)
33,580 (4,640)
40,948 (5,020)
41,840 (5,000)
41,240 (5,345)
12,210 (60); 17,420 (62);
25,715 (188)
12,164 (64); 17,530 (70);
25,861 (164)
250, and 269 8C. The weight loss in this step corresponds to elimination of
benzoylhydrazide anion forming an unstable compound, which decomposes
at 350 8C producing NiO as a final product.
For the complex [Ni(Budtcn)(BeBH)], the TG thermograms (Fig. 5)
show three steps at 180, 200, and 325 8C (DTG). The weight loss at the
first step corresponds to evolution of a CH3CH2CH55CH2 molecule (calc.
13.6%, found 13.5%). For the second step, the weight loss is about 27.5
ꢂ
and the calculated value 27.88% may correspond to loss of the [C7H6NO ]

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Figure 4. TG (——) and DTG (-----) thermograms of [Ni(Etdtcn)(BH)].
radical. The rupture of the N–N bond during thermal decomposition of
hydrazone has been previously reported in the literature.[26] After that, the
unstable complex which is formed decomposes at the final step forming
NiO as a final product.
The thermal behaviour of complexes of the type [M(Rdtcn)(salBH)] is
similar in all compounds (3)–(14), and the TG thermogram (Fig. 6) of
[Ni(Medtcn)(salBH)] is typical. The TG curve of this complex shows three
decomposition steps. The first and second decomposition steps occur at 140
and 275 8C, respectively (DTG curve). The total weight loss for these two
ꢂ
stages is in agreement with the loss of [C7H7NO] (0.5 salBH) radical (calc.
ꢂ
29.9%, found 30.0%), which may abstract a H radical to form [C7H8NO].
Figure 5. TG (——) and DTG (-----) thermograms of [Ni(Budtcn)(BeBH)].

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755
Figure 6. TG (——) and DTG (-----) thermograms of [Ni(Medtcn)(salBH)].
The unstable complex decomposes in the latter step at 325 8C to form NiO as
the final product.
The proposed mechanism of thermal decomposition is illustrated by the
following equation:
ꢀ0:5 SalBH
½NiðMedtcnÞðsalBHÞꢁ ꢀꢀꢀꢀꢀꢀ! ½NiðMedtcnÞðsalBHÞ0:5
ꢁ
ð5Þ
unstable complex
However, expulsion of alkene occurs for alkyl dithiocarbonates, where
alkyl ¼ ethyl,propyl,andbutyltogetherwith0.5moleculeofsalBH.Elimination
of alkenes from alkyl dithiocarbonate was observed in the mass fragmentation
patterns of some alkyl dithiocarbonate complexes.[24]
Mass Spectra
The mass spectral behaviour of the complexes [Ni(Etdtcn)(BH)],
[Ni(Budtcn)(BeBH)], and [Ni(Budtcn)(salBH)] is reported in the schemes of
Figs. 7–9, respectively.
The molecular ion of the two complexes [Ni(Etdtcn)(BH)]þ and
[Ni(Budtcn)(BeBH)]þ is recorded at [Mþ] ¼ 314 and 430, respectively. A
step-by-step decomposition process is proposed, based on the results obtained
in the schemes of Figs. 7 and 8. From these schemes we conclude that a hydra-
zone ligand is lost and its peaks are observed at m/z ¼ 135 [HBH]þ and
m/z ¼ 255 [HBeBH]þ. These ligands lose a nitrogen molecule and in the
ꢂ
two cases the peak at m/z ¼ 105 [C7H5O ]þ[26] results. The second fragment

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Figure 7. The mass spectral behaviour of [Ni(Etdtcn)(BH)].
ꢂ
represents the metal complexes at m/z ¼ 180 [Ni(Etdtcn) ]þ and m/z ¼ 205
ꢂ
[Ni(Budtcn) ]þ, respectively. The aldehyde fragments were detected at
ꢂ
ꢂ
m/z ¼ 44 [CH3CHO ]þ and m/z ¼ 73 [C4H8O ]þ. Also, in the two cases,
ꢂ
ꢂ
there are two peaks at m/z ¼ 136 [Ni(S2CH2) ]þ and m/z ¼ 76 [CS2]þ.
The mass spectral behaviour of some complexes of the type
[M(Rdtcn)(salBH)] (Fig. 9) was also investigated. The complexes seem to
show the same fragmentation patterns for all the studied complexes. The frag-
mentation of [Ni(Budtcn)(salBH)] (Fig. 9) is typical. The mass spectral peaks
Figure 8. The mass spectral behaviour of [Ni(Budtcn)(BeBH)].

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757
Figure 9. The mass spectral behaviour of [Ni(Budtcn)(salBH)].
of the two fragments [C5H10OS2]þ with m/z ¼ 150 (20.4%) and [NiC14H11
N2O2]þ with m/z ¼ 298 (11.9%) represent the two parts of the suggested
ꢂ
formula. In the scheme A of Fig. 9, the fragments [C7H5O ]þ m/z ¼ 105
ꢂ
(36.3%) and [N2]þ m/z ¼ 28 (50.5%) of the HsalBH ligand are detected.
Further fragmentation of the dithiocarbonate moiety is depicted in the scheme
ꢂ
B of Fig. 9. Fragment [C4H8]þ m/z ¼ 56 (100%) represents the alkene mol-
ecule of the alkyl dithiocarbonate, in agreement with the thermal decompo-
sition of these complexes. The final fragment ion m/z ¼ 29 (50.5%)
corresponds to [CH2O]þ.
Microbiological Screening
Benzoylhydrazine, benzaldehyde benzoylhydrazone, salicylaldehyde ben-
zoylhydrazone, some related complexes, and erythromycin (as a reference com-
pound) were tested against a number of bacteria and fungi. The used bacteria
were B. cereus (G þve), P. aeruginosa (G 2ve) and S. aureus (G þve), the
tested fungi were A. flavus, A. fumigatus var. albus, A. niger, F. oxysporum,
and C. tropicum. All samples under investigation were prepared in

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759
500 mg mL21 concentration in DMF as solvent. The culture media were nutrient
agar (NA) media supplemented with 1 g yeast L21. The biological activity of
the ligands and some of their ternary complexes have different activity against
bacteria and fungi. The data listed in Table 4 indicates the following:
1. Erythromycin has no effect on all bacteria and fungi.
2. HsalBH is more active against all bacteria and fungi than the HBH
and HBeBH ligands and their complexes. This activity maybe due
to the OH group of the salicyaldehyde moiety in this compound,
which is subjected to deprotonation in the complexes,[27] but it is
absent in the other two ligands.
3. The activity of some complexes against B. cereus (G þve bacteria)
and A. fumigatus var. allous, A. niger, and C. tropicum maybe due
to the combined effect of metal and dithiocarbonato anion toxicity,
which interact with trace metals of bacteria and fungi.[11] It is
suggested that the neutral mixed-ligand complexes penetrate the
cell wall and dissociate into binary complexes as shown below:
½NiðEtdtcnÞðBHÞꢁ ꢀ! NiðEtdtcnÞþ þ BHꢀ
½NiðBudtcnÞðBeBHÞꢁ ꢀ! NiðBudtcnÞþ þ BeBHꢀ
½MðRdtcnÞðsalBHÞꢁ ꢀ! MðRdtcnÞþ þ salBHꢀ
ð6Þ
ð7Þ
ð8Þ
Thus, the binary complex ions Ni(Etdtcn)þ, Ni(Budtcn)þ, and
M(Rdtcn)þ, act as a toxic agents.[28,29]
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