Synthesis and characterization of chromium(III), molybdenum(II), nickel(II), palladium(II) and platinum(II) complexes, derived from mixed ligands of pyrazole and 2,2-bipyridine

Article abstract of DOI:10.13005/ojc/340343

The recent paper involves the synthesis and characterization studying of chromium(III), Molybdenum(II), nickel(II), palladium(II), and platinum(II) complexes with mixed bidentate ligands namely [3,5-dimethyl-1H-pyrazole-1-carnothioamide and 2,2-Bipyridine] which has been prepared by ring closure of acetylacetone with thiosemicarbazide, in acidified by 2-normality of hydrochloric acid. The new 2-pyrazoline based ligand was identified by mass spectra, NMR and FT-IR spectra. The optimization conditions of pH, time of reaction, and the molar ratio (M:L) were estimated in order to get the pure colored solid complexes chromium(III), molybdenum(II), nickel(II), palladium(II) and platinum(II) by the direct reactions of their metal chlorides in aqueous methanol with the ethanol solution of the ligand. The geometrical structures of the metal complexes were confirmed by measurements of electronic, IR spectra and the detection of magnetic susceptibility and molar conductivity measurements.The octahedral geometry for all complexes was suggested by the results obtained from elemental analyses and other spectral data except that palladium(II) complex which was square-planner in [PdL(bipy)]Cl₂ formula.

Full text of DOI:10.13005/ojc/340343

ISSN: 0970-020 X
CODEN: OJCHEG
2018, Vol. 34, No.(3):
Pg. 1518-1525
ORIENTAL JOURNAL OF CHEMISTRY
An International Open Free Access, Peer Reviewed Research Journal
www.orientjchem.org
Synthesis and Characterization of Chromium(III), Molybdenum(II),
Nickel(II), Palladium(II) and Platinum(II) Complexes, derived
from Mixed Ligands of Pyrazole and 2,2-bipyridine
MAHMOUD NAJM ABID ALJIBOURI1*, ARAF ISMAEL JABBAR2 andTAGHREED M. MUSA3
1Chemistry Department, College of Science, University of Mustansiriyah, Iraq.
2Ministry of Education, Directorate of Education of Anbar, Iraq.
*Corresponding author E-mail: Mahmoud_inor71@uomustansiriyah.edu.iq
http://dx.doi.org/10.13005/ojc/340343
(Received: January 16, 2018; Accepted: March 21, 2018)
ABSTRACT
The recent paper involves the synthesis and characterization studying of chromium(III),
Molybdenum(II), nickel(II), palladium(II), and platinum(II) complexes with mixed bidentate ligands
namely [3,5-dimethyl-1H-pyrazole-1-carnothioamide and 2,2-Bipyridine] which has been prepared
by ring closure of acetylacetone with thiosemicarbazide, in acidified by 2-normality of hydrochloric
acid. The new 2-pyrazoline based ligand was identified by mass spectra, NMR and FT-IR spectra.
The optimization conditions of pH, time of reaction, and the molar ratio (M:L) were estimated in
order to get the pure colored solid complexes chromium(III), molybdenum(II), nickel(II), palladium(II)
and platinum(II) by the direct reactions of their metal chlorides in aqueous methanol with the
ethanol solution of the ligand. The geometrical structures of the metal complexes were confirmed
by measurements of electronic, IR spectra and the detection of magnetic susceptibility and molar
conductivity measurements.The octahedral geometry for all complexes was suggested by the results
obtained from elemental analyses and other spectral data except that palladium(II) complex which
was square-planner in [PdL(bipy)]Cl2 formula.
Key words: Transition metals complexes of 2-pyrazoline, Spectroscopic study of
mixed-ligands of pyrazole, Metal chelates of 2,2-bipyridine.
INTRODUCTION
described and characterized by X-ray crystallography
and the biological studies revealed that the
dimeric design of copper(II) complex modified the
mechanism of oxidation certain types of alcohols4.
As well as the mixed metal complexes of cobalt(II),
copper(II) and zinc(II) derived from 3,5-dimethyl
pyrazole and 8-hydroxy-quinoline was prepared
and fully identified by the single(crystal.X-ray)
The interesting works of coordination
chemistry involving the five-member rings like
pyrazole have been exhibited a great powerful
scaffolds in the novel drugs1-3. The poly nuclear
copper(II), nickel(II) and platinum(II) complexes
derived from poly dentate pyrazole ligands have
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ALJIBOURI et al., Orient. J. Chem., Vol. 34(3), 1518-1525 (2018)
diffraction and NMR spectra5. The antimicrobial
study of gold(III) complexes of 4,4-dihydropyrazole-
1-carbothioamide have adopted6,7 and confirmed
high effective against HeL4 and A549 cell lines.The
increasing effective of mixed ligands incorporating
with pyrazole moiety was described by the presence
of μ-OH, μ-halide, μ- pyrazolate binuclear copper(II)
complexes of 3,5-bis (pyridine-2yl) pyrazole,
by distillation and used.The CrCl3.6H2O, MoCl2.2H2O,
NiCl2.6H2O, K2PtCl4 and Na2PdCl4 solutions were
used without purification and were supplied from
Sigma-Aldrich Company with 99% purity.
Synthesis of 3,5-dimethyl-1H-Pyrazole-1-
carbothioamide
The derivative of pyrazole (L) was prepared
according to the procedure established in literature11.
3-(6-methyl pyridine-2yl-5-(pyridine-2yl) pyrazole8-11
.
Here, the present work described the synthesis of
some transition metal complexes with mixed ligands
of 3,5-dimethyl-1-H-pyrazole-1-carbothioamide and
2,2-bipyridine a secondary ligand.
A solution of (0.91 g, o.o1 mole) of
thiosemicarbazide in (15 ml) hot ethanol was
acidified with 2-3 ml of concentrated HCl, then
(10 ml) of acetylacetone was added with stirring on
water bath for 1 hour. After completing the reaction
through TLC technique, the mixture was kept
overnight in refrigerator to afford white off precipitate
was filtered off, and dried in desiccator overnight,
re crystallized from hot methanol to afford 0.446 g,
70% yield of yellow crystals of the free 2-pyrazoline
primary ligand. The physical properties, and the
elemental analyses were shown in Table (1).
ExPERIMENTAL
Materials and methods
Allthechemicalsusedforsyntheticpurposes
were of Anala Rgrade. Solvents like methanol,
nitric acid, chloroform, dimethyl sulfoxide and ethanol
were purchased from Sigma Aldrich Company and
used as received.Commercial methanol was purified
Scheme 1. Synthesis of 3,5-dimethyl-1-H-pyrazole-1-carbothioamide
Table1: Physical properties and elemental analyses of the L ligand and metal complexes
Compound
Chemical formula
Mwt (g/mole)
Colour
M.P. 0C
M% Obs.
(Calc)
Elemental analysis (%)
Found (Calc.)
%S
C%
H%
N%
L
155
C6H9N3S
469.5
White
168-170
Olive
299-301
Green
310 D
Brown
298 D
Red
-
45.77
(46.42)
5.48
26.90
20.66
(5.86) (27.07) (19.60)
3.90 14.11 5.99
(3.22) (15.00) (6.89)
3.60 14.68 6.88
(3.00) (15.88) (5.88)
3.92 15.89 7.27
(3.11) (16.00) (6.88)
4.00 14.34 5.69
(3.29) (15.08) (5.22)
2.90 12.14 5.44
(2.11) (12.99) (4.79)
[CrL1(L)bipyCl2]Cl
[MoL1(L2)Cl2]
[Ni(bipy)Cl2]
[PdL(bipy)]Cl2
[PtL(bipy)]Cl2
10.77(11.2) 40.96
(93.77)
19.01
(19.66)
12.90
(13.11)
22.01
(22.90)
33.22
C16H17Cl3CrN5S
478.99
C16H17Cl2MoN5S
439.02
C16H17Cl2NiN5S
487
C16H17Cl2PdN5S
576
40.20
(39.99)
44.55
(43.22)
39.5
(38.66)
34.10
(34.00)
277-279
Orange
312D
C16H17Cl2PtN5S
(33.70)

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ALJIBOURI et al., Orient. J. Chem., Vol. 34(3), 1518-1525 (2018)
Synthesis of metal complexes
Dissolve (1 mmole) of CrCl3.6H2O (0.170 g),
with frequency (300MHz) at University of Al-Bait ,
Amman, Jordan.
MoCl2.2H2O(0.2370 g), NiCl2.6H2O(0.456 g), K2PtCl4
(0.596 g) and Na2PdCl4 (0.875 g) in aqueous ethanol
(15-20 ml) then add gradually to stirred warmed
solution of (0.480 g, 2 mmole) of the ligand L1 in
25 ml of methanol. After heating the solution for
15min.,thesecondary2,2-bipydine(1.022g,1mmole)
was added gradually and the mixture was heated
under reflux for three hours with adjusting the pH of
the reaction mixture to about (6.5-8.0) by drops of
ammonia solution and the green crude separated
out, filtered, washed several times with ethanol
and distilled water. The process of reaction was
followed by TLC technique with mixture of solvents
(ethyl acetate: cyclohexane), Table (1).
The magnetic moments of the solid
complexes were determined with Farady’s method
at 300 K temperature on Sherwood Magnetic
susceptibility instrument. The estimation of metals
Cr(III), Ni(II), Pd(II) and Pt(II) in solid complexes were
carried out by flame atomic absorption spectroscopy
through the standard addition method16 on Shimadzu
Corporation Model 6809 at Ibn Cina-Center for
analytical analysis and quality control.
RESULTS AND DISCUSSION
All the mixed complexes of Cr(III), Mo(II),
Ni(II), Pd(II) and Pt(II) formed in solid states with
high melting points and in 1:1:1 of L:bipyridine and
metal ion mole ratios according to the data observed
from carbon, hydrogen, nitrogen and sulfur elemental
analyses. As well as the complexes are insoluble in
common organic solvents like methanol, ethanol,
chloroform, and sparingly soluble in acetonitrile,
whereas it's solubility in DMF and DMSO was greatly,
therefore the measurements of molar conductivity
and electronic spectra were done in DMSO. The
compositions of the prepared compounds were
supported by comparison of their observed (carbon,
hydrogen, and nitrogen) elemental analysis with the
calculated values, Table(1).
Physical measurements
The elemental analyses (C. H. N. S) were
carried out on EuroEA-Element Analyzer 3000, at
College of Education of Pure Science Ibn-Al-haithum,
University of Baghdad. The electronic spectra were
recorded in ethanol and DMF. The FT-IR spectra
of the complexes and the free primary ligand (L)
were scanned in the range (4000-400) cm-1 by their
thin KBr and CsI discs. The mass spectra for the
prepared compounds were recorded by electron
impact mass spectrometry (EIMS) using a Direct
Injection Probe on a Shimadzu GCMS – QP 2010
Spectrometer, At College of Science, Department
of Chemistry, Mustanseriyah University.The 1H and
13C NMR spectra were recorded in d6-DMSO as a
solvent using a Bruker DMX-500 NMR spectrometer
Mass spectra
The secondary ligand according to the
literature has molecular ion m/e=162 and this peak was
obviously resulted from MS spectra in Figure (1). The
hygroscopic effect was observed in the molecular
ions of bipyridine secondary ligand.
Fig. 1. Mass spectra of the secondary ligand 2,2'-bipyridine

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ALJIBOURI et al., Orient. J. Chem., Vol. 34(3), 1518-1525 (2018)
The Fig. (2) showed a molecular ion
mle=155 with relative intensity of 100% indicating the
base peak and high stability of C6H9N3S+. and this
data supports strongly the formula and structure of
the primary ligand (L). The other fragments around
m/e=95 with 65% intensity reveals the cleavage of
H2N-C=S moiety or cleavage of two methyl groups
to afford the pyrazole ion with good stability. As
well as the Fig. (3) shows the MS spectra of Cr(III)
complex and the molecular ion m/e=486 reveals the
empirical formula of the expected structure in which
one mole of primary pyrazo;e ligand would be binded
by coordination bond to chromium(III) ion beside one
mole of a secondary 2,2-bipyridine ligand bonded
through two nitrogen atoms .The fragmentations of
–Cl in the first step of proposed mechanism in MS
spectra confirms the presence of counter ion as Cl-1
and the several peaks around 380, 360 and 290 may
be assigned to the cleavage of -2Cl, -C10H8N2 and
H2N-C=S moiety respectively.
Fig. 2. Mass spectra of the primary ligand L
Fig. 3. Mass spectra of [CrL(bipy)Cl2]Cl complex
NMR Spectra
The 1H NMR spectra of the primary
ppm and 7.65 ppm may be ascribed to –CH=C-
and the tautomeric –N-H- with –S-H thiol form in
deuterated DMSO solution, Fig. (4). As well as the
carbon-13 NMR spectra of the primary pyrazole
ligand in CDCl3 solvent exhibited symmetric peaks
around 145, 106 and 11.20 ppm which are assigned
to the resonance peaks of –C=S ,CH=C-N- and –CH3
therefore confirms the structure of the ligand and
agree well with the data observed in literature14.
ligand in CDCl3 showed singlet peak at 2.49 ppm
assigning to 6H of two methyl groupd attached
directly to pyrazole ring at 3 and 5 positions. As well
as the de shielded –NH2- protons was appeared
as singlet absorption around 12.187 ppm and this
confirms the ring closure of the starting materials of
acetyl acetone with thiosemicarbazide in methanol
solution. Furthermore the peaks in the regions 6.10

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ALJIBOURI et al., Orient. J. Chem., Vol. 34(3), 1518-1525 (2018)
Fig. 4. H NMR spectra of the ligand (L) in CDCl3 solvent
Fig. 5. 13C NMR spectra of the ligand (L) in CDCl3 solvent.
F.T. I. R. Spectra
The observation of new bands around
1530-1518 cm-1, 1480-1420, and 13200-1240
cm-1 may be assigned to –C=N- and –C=C—and
–C=S moieties of pyrazoline and thioamide
groups respectively, then revealed the formation
of five-member ring with ions of chromium(II),
molybdenum(II), palladium(II), and platinum(II).
The broad bands around 3500-3200 cm-1 besides
the bending of coordinated water molecules in the
regions 1560-1550 cm-1, and 845-822 cm-1 supported
the –OH coordinated by water in the inner sphere
of metal complexes17. Furthermore, the infrared
spectra of the nickel(II) complex showed weak to
medium bands around 250-375 cm-1 supporting
(3400-3290), and (1610-1598) cm-1 assigned
to the asymmetric and symmetric modes of
–NH2- and the absorptions of imine-C=N- of
pyrazole ring respectively13,14. It is obviously that
the FT-IR spectra of all metal complexes showed
remarkable changes in the positions and intensities
of the imine-C=N-, -C=S and –NH- groups which
confirmed the participation of the nitrogen and
sulphur atoms of pyridyine and carbothioamide in
N2- and N1- in coordination with the metal ions16,17,18
The appearance of strong absorptions in the regions
.

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ALJIBOURI et al., Orient. J. Chem., Vol. 34(3), 1518-1525 (2018)
Zn-Cl bonds. The lower frequency regions of IR
spectra of all complexes recorded weak bands
around (455-560) cm-1 and (400-388) cm-1 that are
the bidentate behavior of the ligand through two
nitrogen atoms of pyrazoline and pyridine rings,
thereby gives strong proof for the metal complexes
formation and kinetic stability of the five-member ring
chelate with the selected bivalent metals18.
attributed to M-N and M-S bonds respectively17,18
The data obtained from FT-IR spectra investigated
.
Table 2: IR spectra n cm-1of the ligand (L) and it’s metal complexes
Compound
L
n(N-H) cm-1
3420,3180(m) 1600-1596(s)
n(C=N) cm-1
n(C=S) cm-1
1254(m)
870(s)
n(M-N)
n(M-S)
-
-
Cr-L
Mo-L
3390(br)
3420,3100(m)
1533(sh)
1549(s)
1238(m)
1230(s)
855(m)
1225(m)
865(m)
1222(s)
870(s)
488(w)
422(m)
412(w)
388(w)
Ni-L
Pd-L
Pt-L
3217(m)
3333(br)
3197(m)
11580(s)
1575(s)
1528(s)
500(w)
512(m)
560(w)
435(w)
410(w)
450(m)
1240(m)
827(m)
br=broad, m=medium, s=strong, sh=shoulder and w=weak.
UV-Visible spectra and magnetic measurements
of the type 1A1g→ 1B1g and 1A1g→ 1B2g
respectively24. The diamagnetic properties of
Pd(II) and Pt(II) complexes indicates the low-spin
state for the square-planner (n-1)d8 configuration
then ascribed their electronic transitions in the
The UV-Vis spectrum of the free ligand
of pyrazole-carbthioamide in methanol displayed
two peaks at 50000 and 32258 cm-1 ascribing to
the moderate energy p→p* and n→p* respectively
associating with the functional groups of transition
C=N- and -C=S moiety17,18.The solutions of metal
complexes in DMF solvent (10-3 M) display spin-
allowedabsorptionsinthevisiblereginassigningtothe
d-d spectra of the metal ions involved in the structure
of the prepared complexes. The green solution of
Cr(III) complex showed two weak bands around
10527, 16666 cm-1 supporting the octahedral
environment around Cr(III) ion. As well as the
intense peak at 28985 cm-1 is belonged to LMCT
then confirm the proposed structure of Cr(III)
complex20,21. By the same way the molybdenum(III)
complex in DMF showed there bands around 13333,
20832 and 31055 cm-1 confirming the d-d spectra of
Mo(II) octahedral complexes20,21.The paramagnetic
properties of Cr(III) and Mo(II) complexes with
magnetic momentums values (3.8-3.90 ) BM assist
in the elucidation their structures21-23. As well as the
olive solution of nickel(II) complex in DMF exhibited
two spin-allowed transitions at 12048 and 27027 cm-1
which supports the high-spin of 3d8 configuration.
The orange and yellow solutions of palladium(II)
and platinum(II) complexes in DMF displayed
(29761-36363) cm-1 and (17543 -23094 ) cm-1
UV-Visible25,26
.
Table 3: Electronic spectra ,molar conductivity
and magnetic moments of the complexes
Compound λ max (nm) u cm-1 Λohm-1. μ B.M.
cm2.mol-1
L
310
Cr-L
250
32258
600
450
300
750
480
322
835
370
336
275
570
433
50000
-
-
10527
16666
28985
13333
20832
31055
12048
27027
29761
36363
17543
55
3.88
Mo-L
12
3.9
Ni-L
Pd-L
Pt-L
22
89
3.22
0
17
23094
0
Λ=molar conductance in DMSO solutions of 0.001M
concentration.
assigning to the spin-allowed of (n-1)d8 configuration

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ALJIBOURI et al., Orient. J. Chem., Vol. 34(3), 1518-1525 (2018)
Scheme 3. Geometrical structures of the prepared metal complexes
Effect of pH on the formation of metal complexes
The UV-Vis spectra of Molybdenum(II)-ligand
mixed solution with a concentration range of
(2*10-3-1*10-3) M were studied.The concentration of
(2*10-3 )M was obeyed the Lambert-Beer's law and
showed a clear intense color. A straight line, with
correlation factor (r = 0.98), was obtained when the
absorbance plotted against the molar concentration,
as well as the investigation of 2:1 molar ratio of
the ligand to metal ion in methanolic solution after
adjusting the acidity of mixture and the absorption
of d-d regarding molybdenum(II)-L complex at 835
nm27.
were isolated in the solid state after optimization the
conditions of time, acidity, and the molar ratio. The
active sites of the ligand in bonding with the metal
ions are the two atoms of nitrogen 2N of pyrazole
ring and sulfur atom of thiocarbamide moiety then
proposing a kinetic stable five member ring and
the suggested geometry of the chromium(III) and
molybdenum(II) were octahedral in the formulas
[Cr(L)(bipy)Cl2]Cl and [Mo(L)(bipy)Cl2] respectively.
However, the square-planner geometry was obtained
for palladium(II) and platinum(II) complexes with
[ML(bipy)]Cl2 formula.
ACKNOwLEDGMENT
CONCLUSION
We are so grateful to the members work in
the service laboratories at Chemistry Department,
College of Science, University of Mustansiriyah
for facilitating the measurements of the FT-IR,
UV-Visible,massspectra,magneticsusceptibilityandthe
molarconductivity.Aswellas,weappreciatedtheefforts
of Al-Bait university for analysis of NMR spectra.
According to the results obtained from
elemental analyses, proton nmr, IR, mass spectra
and magnetic moments the new derivative of
2-pyrazoline behaved as bi dentate ligand toward
the chromium(III), molybdenum(II), nickel(II),
palladium(II) and platinum(II) ions.The all complexes
REFERENCES
1.
2.
3.
4.
T.L.Jacobs, inR.C.Elderfield, Ed., Hetrocyclic
compounds, John Wiley and Sons, Inc., New
York., 1957, 45, 5.
Sharma, P. K., Kumar S., Kumar. P., Kaushik.
P., Daushik, D., Dhingra,Y., Aneja, K. R., Eur.
J. Med. Chem., 2010, 45, 2650-2655.
Saugata, K. Atanu ,J. Kinsuk ,D. Sangita, R.
Sudipta, C. James, A. Arnold, L. Rheingold, S.
Kumar, K. Polyhedron., 2011, 30, 2801-2808.
Guo-Fang Zhang, Qiu-Ping Zhou, Yin-
Li Dou, Mai-Hua Yin and Yao Wang ”
Synthesis, structural characterization and
catalytic activities of dicopper(II) complexes
derived from tridentate pyrazole-based N2O
ligands” Appl. Organometal. Chem., 2007, 21,
1059–1065.
5.
Saugata, K. Atanu ,J. Kinsuk ,D. Sangita, R.
Sudipta, C. James, A. Arnold, L. Rheingold
and S.Kumar, K.”Synthesis, crystal structure,
spectroscopicandphotoluminescencestudies
of manganese(II), cobalt(II), cadmium(II),
zinc(II) and copper(II) complexes with
a pyrazole derived Schiff base ligand,
Plyhedron., 2011, 30, 2801-2808.
Frankiine K. Keter, Stonard Kanyanda,
Syvester S. L. Lyantagaye, James Darkwa,
D. Jasper G.Rees and Mervin Meyer “
In vitro evaluation of dichloro-bis(pyrazole)
6.

1525
ALJIBOURI et al., Orient. J. Chem., Vol. 34(3), 1518-1525 (2018)
palladium(II) and dichloro-bis(pyrazole)
platinum(II) complexes as anticancer agents”,
Cancer Chemother Pharmacol., 2008,
63,127-138.
Shuxiang, W.Wenquing, S.Hongdong, L.Cui,
L.Wang, K.Zhang, J.Eur. J. Med. Chem.,
2011, 46, 1914-1918.
Attila,K.Denes,N.Gyorgy,P.Katalin,M.Vukadin,
M.Zeljko, J.Ivan, R.Judith, H.Zoran, D.Gerald,
G. J.Chem., 2005, 29,833-840.
Bogulmila,Krysztof,S.Katarzyna,M.Kamila,K.
Malgorzata,C.Keppler,B.Budzsz,E. Med.
Chem. Res., 2013, 22, 2395-2402.
Kishwar,S.W.Waseem,L.Mohamad,H.Ming,
J.Mohamad,Imran, A. Future Med.Chem.,
2013, 5(2), 135-146.
Z.Marczenko, “Spectrophotometric
determination of elements”, John Wiley and
Sons, 1st Ed.1976.
Sau, D.K.Butcher, R.J.Chudhuri and S.Saha,
N.”spectroscopic, structural and antibacterial
properties of copper (II) complexes with
bio-relevant 5-methyl-3-formyl pyrazol-N(4)-
benzyl-N(4) methyl thiosemicarbazone” Mol.
Cell. Biochem., 2003, 253, 21-29.
Jons, J. Sanchez, F. J. Labarta , A.
Casabo, J. Texido and F. Caubet , A. “Mixed
bridged ,dinuclear copper(II) complex with
dinuclearingpyrazole derived ligand” Inorg.
Chim. Actc.,1993, 208, 167-171.
Luisa, M.D.Martinsa, R.S.Armandao,
J. Pombeira and L. Water-Soluble
C-Scorpionate Complexes – Catalytic and
Biological Applications, Eur. J. Inorg. Chem.,
2016, 2, 2236-2252.
Hiroshi Maruoka, Sho Nishida, Nobuhiro
Kashige, Yuki Yoshimura, Masahiko Omori,
Ryoko Tomita, Eiichi Masumoto, Fumi
Okabe,Fumio Miake, Kenji Yamagata and
Toshihiro Fujioka” Synthesis and Biological
Activity of Some New Pyrazole Copper(II)
Complexes, J. Heterocy. Chem., 2012,
49,1218 -1223.
Silverstein, R.M.Webster and F. Kienle, D.J.
“Spectrometric Identification of Organic
Compounds”, John Wiley & Sons, USA. New
York,1984.
Hai-Bin, S.Shun-Jun and J. Bing, B. “Studies
on transition metal ions recognition properties
of 1-(2-benzothiazole)-3-(2-thiophene)-2-
pyrazoline derivatives, Dyes & Pigm., 2007,
73, 394-396.
Saled M. Khalil “Synthesis, Spectroscopic
and Magnetic studies on metal complexes
of 5-methyl-3-(2-hydroxy phenyl pyrazole”,
J. Coord. Chem., 2003.
Mishra, R.C., “synthesis and physic-
chemical studies of some novel mixed-
ligand cyanonitrosyl{CrNO}5 complexes
of chromium(III) with 2-pyrazoline-5-one
derivatives”, Transition Met. Chem. 1987,12,
551-552.
Nakamato K."Infrared&Raman spectra of
Inorganic and Coordination Copounds"5th.
Edn.John &Wiley Sons, New York,1998,
183-187.
Sian C. Davies, Marcus C. Durrant , David
L. Hughes, Abbas Pezeshk, Raymond L.
Richards,” Coordination chemistry of a
pyrazoline derived from 2,4-pentanedione
bis(4-methylthiosemicarbazone) Crystal
structure of the pyrazoline and evidence
formetal-mediated ring opening”, J. Chem.
Research, 2011,100–103.
Huheey, J.E;"Inorganic Chemistry, Principles
ofStructureandReactivity"Harper.International
51 Edittion; Maryland,1994.
Green Wood, N. N.Earnshow, A. “Chemistry
of the Elements”, Ed. J.Wiley, Sons. Inc.New
York,1998.
D.Sutton"ElectronicSpectraofTransitionMetal
Complexes "McGraw Hill, New York, 1968.
Saugata, K. Atanu ,J. Kinsuk ,D. Sangita, R.
Sudipta, C. James, A. Arnold, L. Rheingold,
S. Kumar, K.” Synthesis, crystal structure,
spectroscopicandphotoluminescencestudies
of manganese(II), cobalt(II), cadmium(II),
zinc(II) and copper(II) complexes with
a pyrazole derived Schiff base ligand,
Plyhedron, 2011, 30, 2801-2808.
Attila, K.Denes, N.Gyorgy, P.Katalin, M.
Vukadin, M.Zeljko, J.Ivan, R.Judith, H.Zoran
and D. Gerald, G. “Structural, spectroscopic
and computational studies of the HgL2Cl2
complex (L= 3,5-dimethyl-1-thiocarboxamide
18.
19.
7.
8.
9.
20.
21.
10.
11.
12.
22.
23.
13.
14.
15.
24.
25.
26.
27.
pyrazole) and the crystal structure of L New”
J. Chem. 2005, 29, 833-840.
Frankiine K. Keter, StonardKanyanda,
Syvester S. L. Lyantagaye, James Darkwa,
D. Jasper G.Rees and Mervin Meyer “In
vitro evaluation of dichloro-bis(pyrazole)
palladium(II) and dichloro-bis(pyrazole)
platinum(II) complexes as anticancer agents”,
Cancer Chemother Pharmacol., 2008, 63,
127-138.
16.
17.