Transition metal chelates: Synthesis, physicochemical, thermal, and biological studies

Article abstract of DOI:10.1134/S1070363216040241

The transition metal complex of Mn(II), Co(II), Ni(II), Cu(II), Ti(III), Cr(III), Fe(III), Zr(IV), and UO₂(VI) ion with a Schiff’s base ligand derived from 2-hydroxy-[2-oxo-1,2-dihydro-3H-indol-3-ylidene]-benzohydrazide have been prepared. The complexes have been characterized by elemental analysis data, IR and electronic absorption spectra, magnetic moments, and thermogravimetric analysis data. The complexes of the 1: 1 metal-to-ligand stoichiometry have been formed. The physico-chemical data have suggested the octahedral geometry for all the complexes except for Cu(II); the Cu(II) complex has been square planar. Thermal analysis data of the ligand and its complexes have been analyzed, and the kinetic parameters have been determined using the Horowitz–Metzger method. According to the solid-state electrical conductivity measurements, the ligand and its complexes are semiconducting in nature. The antimicrobial activity of the ligand and the complexes towards E. coli, S. typhi, P. aeruginosa, and S. aureus has been tested by the disc diffusion method.

Full text of DOI:10.1134/S1070363216040241

ISSN 1070-3632, Russian Journal of General Chemistry, 2016, Vol. 86, No. 4, pp. 901–906. © Pleiades Publishing, Ltd., 2016.
Transition Metal Chelates:
Synthesis, Physicochemical, Thermal, and Biological Studies
1
a
b
b
b
N. J. Suryawanshi , G. B. Pethe , A. R. Yaul , and A. S. Aswar
a
Department of Industrial Chemistry, Arts, Science and Com. College, Chikhaldara, 444807 India
e-mail: aswar2341@rediffmail.com
b
Department of Chemistry, Sant Gadge Baba Amravati University, Amravati, 444602 India
Received May 10, 2015
Abstract—The transition metal complex of Mn(II), Co(II), Ni(II), Cu(II), Ti(III), Cr(III), Fe(III), Zr(IV), and
UO (VI) ion with a Schiff’s base ligand derived from 2-hydroxy-[2-oxo-1,2-dihydro-3H-indol-3-ylidene]-
2
benzohydrazide have been prepared. The complexes have been characterized by elemental analysis data, IR and
electronic absorption spectra, magnetic moments, and thermogravimetric analysis data. The complexes of the
1
: 1 metal-to-ligand stoichiometry have been formed. The physico-chemical data have suggested the
octahedral geometry for all the complexes except for Cu(II); the Cu(II) complex has been square planar.
Thermal analysis data of the ligand and its complexes have been analyzed, and the kinetic parameters have
been determined using the Horowitz–Metzger method. According to the solid-state electrical conductivity
measurements, the ligand and its complexes are semiconducting in nature. The antimicrobial activity of the
ligand and the complexes towards E. coli, S. typhi, P. aeruginosa, and S. aureus has been tested by the disc
diffusion method.
Keywords: hydrazone, Schiff’s base, thermal analysis, electrical conductivity, antimicrobial activity, scanning
electron microscopy
DOI: 10.1134/S1070363216040241
Studies of the Schiff’s bases and their metal com-
plexes have contributed much to the development of
coordination chemistry. These compounds are of
special importance in view of diverse applications in
various branches of modern applied chemistry. Transi-
tion metal complexes of hydrazones of the Schiff’s
bases have been among the most widely studied
coordination compounds over the past few decades.
The coordination chemistry of transition metal com-
plexes of hydrazones has been intensively investigated
due to their biological activity [1] giving rise to their
application in the treatment of tuberculosis [2], mental
disorders, and tumors [3, 4]; on top of that, they are
also known as herbicides and insecticides [5].
Hydrazones have been recognized as analytical
reagents for determination of metal ions [6, 7]. In the
view of the importance of hydrazones, in this work we
prepared the Schiff’s base of 2-hydroxy-1-(2-hydroxy-
The complexes were colored solids stable in air and
insoluble in water as well as in most of the common
organic solvents. The physico-chemical data including
elemental analysis results, color, electrical conduc-
tivity, and activation energy of the compounds decom-
position are collected in Table 1. The results indicated
the formation of the 1 : 1 (metal : ligand) stoichiometry
for all the complexes.
IR spectra of the complexes were compared with
that of the free ligand. The free ligand spectrum
–1
contained a band at 1710 cm assigned to the ν(C=O)
mode of the isatin moiety and of the hydrazone amide
group [8]. The band due to the ν(C=N) vibration
–1
appeared at 1639 cm . The isatin ν(C=O) band of the
complexes was shifted towards lower frequency by 9–
–1
2
2 cm due to the coordination of the C=O group at
the metal ion. The ν(C=N) band was shifted to lower
–1
frequencies by 10–32 cm , thus indicating the coor-
5
-methyl-3-nitrophenyl)ethylidene]benzohydrazide and
dination of azomethine nitrogen at the metal ion. A
studied its complexes with Mn(II), Co(II), Ni(II),
–1
broad band observed at 3260 cm was assigned to the
Cu(II), Ti(III), Cr(III), Fe(III), Zr(IV), and UO (VI).
2
hydroxyl group of isatin involved in the intramolecular
hydrogen bonding with the NH group. The amide
ν(C=O) band was absent in the spectra of all the
complexes, and a new band of the ν(C–O) appeared at
1
The text was submitted by the authors in English.
9
01

9
02
SURYAWANSHI et al.
Table 1. Analytical data of ligand and its complexes
Elemental analysis, wt %
found calculated
Electrical Activation
conductivity, energy,
Compound
Color
–1
–1
Ω cm
eV
M
–
C
H
N
M
–
C
H
N
L
Orange
64.22 4.02 14.75
64.05 3.94 14.94
–
–
–
10
[
[
Mn(L)Cl·H
Co(L)Cl·H
2
O]
2
Black-brown 14.03 46.18 3.02 10.76 14.14 46.36 3.11 10.81 4.36 × 10
0.178
0.220
–
9
2
O]
2
Greenish red 14.87 45.76 3.01 10.62 14.87 45.88 3.08 10.70
5.88 × 10
–
11
[
[
Ni(L)Cl·2H
Cu(L)]Cl
2
O]
Dark gray
10.11 43.75 3.19 10.16 10.24 43.89 3.44 10.24 3.89 × 10
16.58 47.37 2.54 10.97 16.76 47.50 2.66 11.08 1.31 × 10
0.150
0.084
–12
2
Greenish
brown
–
–
–
11
12
10
[
[
[
[
[
Ti(L)Cl
2
·H
2
O]
Pale yellow 11.36 43.11 2.83 9.95 11.48 43.20 2.90 10.08 4.67 × 10
Dark brown 16.78 42.65 2.70 9.81 16.84 42.78 2.87 9.98 2.18 × 10
Olive brown 13.03 42.27 2.74 8.75 13.03 42.39 2.85 9.89 1.12 × 10
0.327
0.193
0.330
0.204
0.110
Cr(L)Cl
2
·H
·H
2
O]
Fe(L)Cl
2
2
O]
–
9
Zr(OH)
3
(L)CH
3
OH] Musk yellow 18.58 44.15 3.17 9.54 18.63 44.18 3.26 9.67
5.62 × 10
–
12
UO (L)CH
2
3
OH]NO
3
Reddish
yellow
33.85 29.74 2.10 8.56 36.94 29.82 2.19 8.70 1.20 × 10
–
1
1
092–1120 cm , evidencing about enolization of the
absorption spectral and the determined magnetic
carbonyl group in the course of the complex formation.
Furthermore, IR spectra of the metal complexes lacked
the ν(NH) absorption band, but exhibited a strong band
moment of 6.02 µ suggested the octahedral geometry
B
of the Mn(II) ion [14, 15]. The Co(II) complex
–1
exhibited three peaks at 10309, 16286, and 24154 cm ,
–
1
4
4
4
4
at 1607–1629 cm due to the vibrations of the –C=N–
N=C– moiety [9]. Hence, the ligand likely acted as a
singly-charged tridentate chelating agent coordinated
at the central metal ion via azomethine nitrogen, the
enol oxygen, and the isatin carbonyl oxygen atoms.
The spectra of uranyl and Zr(IV) complexes contained
assigned to the T (F)→ T (F), T (F)→ T (P), and
1g 2g 1g 1g
4
4
T (F)→ A (F) transitions, respectively; that was
1
g
2g
indicative of the octahedral environment of the central
Co(II) ion [16]. The ligand field parameters of the
metal–ligand bond in the Co(II) complex were
–
1
determined [Δq of 548 cm , the Racah interelectronic
–
1
–1
a band at ≈950 cm due to the presence of methanol,
repulsion parameter (β') of 634 cm , the nephelauxetic
–
1
and the band observed at 927 cm in the spectrum of
ratio (β) of 0.65, and ν /ν of 1.57]. The Racah inter-
1
2
the uranyl complex was assigned to the ν (O=U=O)
electronic repulsion parameter for the complex was
as
–
1
mode [10–12]. The coordination of H O in the Mn(II),
lower than that for the free ion (971 cm ), suggesting
delocalization of the metal electron over the metal and
the ligand i.e. the significant covalent character in the
metal–ligand bond. The magnetic moment value for
2
Co(II), Ni(II), Ti(III), Cr(III), and Fe(III) complexes
was indicated by the appearance of the absorption
bands at 3218–3356 [ν(OH)], 1502–1547 [δ(H O)],
2
–
1
and 806–842 [ρ(H O)] cm . In addition to above
the Co(II) complex was of 4.82 µ , suggesting the
2
B
bands, all the complexes showed the absorption bands
high-spin octahedral type complex type. The Ni(II)
complex exhibited three spectral bands at 10559, 17006,
in the far-infrared region: 502–557 [ν(M–O)] and 442–
–
1
–1
3
3
4
90 [ν(M–N)] cm [13].
and 26246 cm corresponding to the A (F)→ T (F),
2g 2g
3
3
3
3
A (F)→ T (F), and A (P)→ T (P) transitions,
2
g
1g
2g
1g
The electronic absorption spectral data and magnetic
respectively, revealing the octahedral geometry around
Ni(II) ion [17]. The ligand field parameters of the
metal–ligand bond in the latter complex were
moment values were further studied to determine the
complexes geometry. In particular, the Mn(II) complex
–1
–1
exhibited three bands at 17482, 24213, and 26954 cm ,
determined [Δq of 1055.9 cm , the Racah inter-
6
4
4
6
4
4
–1
assigned to the A → T ( G), A → T ( G), and
electronic repulsion parameter (β') of 771.66 cm , the
1
g
1g
1g
2g
6
4
A → E , transitions, respectively. The electronic
nephelauxetic ratio (β) of 0.74, and ν /ν of 1.61], the
1
g
g
1
2
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 4 2016

TRANSITION METAL CHELATES
903
fraction of the covalent character of the bond being of
5.23%. The Racah inter-electronic repulsion
2
parameter for the complex was again lower than that
for the free ion, suggesting the electron density
delocalization between the metal ion and the ligand.
The ν /ν ratio was in the range of the octahedral Ni(II)
1
2
complexes. The magnetic moment value for the Ni(II)
complex was of 3.13 µ , suggesting the octahedral
B
surrounding of the metal ion. The Cu(II) complex
–
1
showed three bands at 15267, 17214, and 19920 cm
2
2
2
2
corresponding to the B → A , B → E , and charge
1g
1g
1g
g
transfer transitions, respectively, evidencing about the
square planar Cu(II) complex geometry [18]. The
magnetic moment value of Cu(II) complex was of
1
.30 µ . The unusual magnetic moment value might be
B
owing to the metal–metal interaction in the dimeric
structure. The Ti(III) complex showed a broad band at
–
1
2
2
1
8315 cm likely related to the T → E transition of
2g g
the octahedral geometry of the Ti(III) ion. The
magnetic moment of the Ti(III) complex was of
1
.62 µ , corresponding to one unpaired electron in the
B
octahedral surrounding of the ion. The Cr(III) complex
Temperature, °C
Fig. 1. Thermograms of the ligand and its complexes.
(1) Ligand, (2) Mn(II), (3) Co(II), (4) Ni(II), (5) Cu(II),
–
1
exhibited three characteristic bands at 18115 cm (ν ),
1
–
1
–1
2
4449 cm (ν ), and 38910 cm (ν ) assigned to the
A (F)→ T (F), A (F)→ T (F), and A (F)→ T (P)
2 3
4
4
4
4
4
4
2
(6) Ti(III), (7) Cr(III), (8) Fe(III), (9) Zr(IV), and (10) UO (VI).
2g
2g
2g
1g
2g
1g
transitions, respectively. The ligand field parameters of
the metal–ligand bond in the latter complex were
–
1
results are shown in Fig. 1. The TG curves revealed
three-stage decomposition pattern for the Mn(II),
Co(II), Ni(II), Ti(III), Cr(III), and Fe(III) complexes
and two-stage decomposition in the case of the free
determined [Δq of 1811 cm , the Racah inter-elec-
–
1
tronic repulsion parameter (β') of 600 cm , the
nephelauxetic ratio (β) of 0.652, and ν /ν of 1.35], the
1
2
fraction of the covalent character of the bond being of
.48%. The Racah inter-electronic repulsion parameter
2
+
ligand as well as the Cu(II), Zr(IV), and UO2
3
complexes. The mass loss corresponding to two [the
Mn(II), Co(II), and Ni(II) complexes] or one [Ti(III),
Cr(III), and Fe(III) complexes] coordinated water
molecules was observed in the first step (160–210°C)
for the complex was again lower than that for the free
ion, suggesting the electron density delocalization
between the metal ion and the ligand [19].The ν /ν
ratio of 1.34 was very close to the value of 1.42
obtained for the purely octahedral Cr(III) complexes
2
1
[the observed/calculated mass loss was of 4.80/4.63,
Mn(II); 4.67/4.58 Co(II); 8.92/8.77, Ni(II); 4.19/4.31,
Ti(III); 4.39/4.27, Cr(III); 4.37/4.23, Fe(III) (wt %)].
The Ti(III), Cr(III), and Fe(III) complexes were stable
up to 290°C, showing gradual weight loss at further
heating up to ≈470°C, corresponding to the loss of the
coordinated ligand [25]. The Ti(III), Cr(III) and Fe(III)
complexes were almost stable up to 220°C, indicating
the absence of lattice or coordinated water molecules.
In the cases of Mn(II), Co(II), Ni(II), Cu(II), Ti(III),
Cr(III), and Fe(III) complexes, rapid mass loss was
observed over 290–470°C, assigned to the loss of the
organic part of the coordinated ligand. Further heating
was accompanied by gradual weight loss corres-
ponding to the decomposition of the remaining part of
[
20, 21]. The magnetic moment value of 3.94 µB
further evidenced about the octahedral geometry of the
Cr(III) ion [22]. The Fe(III) complex exhibited three
spectral bands at 13679, 17857, and 22883 cm
–
1
6
4
6
4
assigned to the A → T (G), A → T (G), and
1
g
1g
1g
2g
6
4
4
A → E , T (G), transitions, respectively, corres-
1
g
g
1g
ponding to the octahedral geometry around Fe(III) ion
23]. The magnetic moment was of 5.88 µ , indicating
[
B
2+
high-spin state of the complex. The Zr(IV) and UO2
complexes were diamagnetic, as expected from their
electronic configuration [24].
In order to investigate the stability of the com-
plexes, the TG analysis was carried out; the basic
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 4 2016

9
04
SURYAWANSHI et al.
Table 2. Thermal decomposition data of ligand and its complexes
Temperature
Activation
of half-
Free energy
change ΔG ,
Frequency factor Z,
Entropy change
ΔS , J mol K
#
Compound
energy E
a
,
–1
#
–1
–1
decomposition,
s
kJ/mol
kJ/mol
°C
–
–
–
–
–
–
–
–
–
–
3
2
3
2
2
3
3
3
2
3
L
303
304
386
348
414
372
408
316
366
384
18.16
24.17
21.04
19.27
26.17
26.16
20.38
21.36
24.53
23.44
7.63 × 10
4.61 × 10
3.36 × 10
3.15 × 10
2.59 × 10
4.16 × 10
3.18 × 10
5.15 × 10
3.15 × 10
3.17 × 10
263.47
241.53
234.48
255.63
229.47
256.39
208.35
217.26
183.57
192.11
184.37
150.46
174.43
164.68
185.43
194.54
176.77
165.70
188.64
157.87
[
[
[
[
[
[
[
[
[
Mn(L)Cl·H
Co(L)Cl·H
Ni(L)Cl·2H
Cu(L)]Cl
Ti(L)Cl ·H
2
O]
O]
O]
2
2
2
2
2
2
2
O]
Cr(L)Cl
2
2
·H
2
O]
Fe(L)Cl
·H
2
O]
Zr(OH)
3
(L)CH
3
OH]
UO (L)CH
2
3
OH]NO
3
2
+
the coordinated ligand. The high-temperature residue
was the corresponding metal oxide [the observed/
calculated mass loss: 19.94/19.62 (Mn O ); 21.32/20.44
Cr(III) > Co(II) > UO2 > Ti(III) > Zr(IV) > Ni(II) >
Fe(III) > Mn(II) > free ligand series.
3
4
The Horowitz–Metzger method [26] was used to
determine the kinetic parameters of the compounds
thermal decomposition. The negative values of ΔS
suggested the higher ordered activated state that might
be formed via chemisorption of oxygen and/or decom-
position products. No definite trend in the E values
(
Co O ); 18.66/18.19 (NiO); 21.87/21.46 (CuO); 19.26/19.14
3 4
(
TiO ); 18.19/18.04 (Cr O ); 18.89/18.78 (Fe O );
#
2
2
3
2
3
2
7.30/25.14 (ZrO ); and 43.85/43.46 (U O ) wt %].
2 3 8
The thermal stability of the studied complexes (as
determined by the temperature of the 50% degree of
decomposition, Table 2 followed the Cu(II) >
a
(
ranging in between 18.16 and 26.17 kJ/mol) was
observed.
–1
–1
log σ, Ω cm
The solid-state d.c. electrical conductivity of the
complexes in the form of the compressed pellets
Table 1) increased with temperature following the
(
Arrhenius equation [27] (Fig. 2); the corresponding
activation energy values are given in Table 1 as well.
The increase in the conductivity started when charge
carriers had gained enough of the energy to overcome
the activation barrier; that reflected the property of a
typical semiconductor [27]. The electrical conductivity
1
2
3
4
–
12
of the complexes ranged in between 1.20×10 and
–
9
–1
–1
5
.88 ×10 Ω cm , and the values measured at 373 K
7
5
6
8
followed the Co > Zr > Mn > Fe > Ti > Ni > Cr > Cu >
UO series.
2
9
The ligand and its metal complexes were screened
for the antibacterial activity against E. coli, S. typhi, P.
aeruginosa, and S. aureus; DMSO was taken as
reference. The results showed that the ligand exhibited
the larger inhibition zone against E. coli and P.
aeruginosa. All the complexes except for those of
–
1
1
000/T, K
Fig. 2. Electrical conductivity of the complexes as function
of temperature. (1) Ni(II), (2) Zr(IV), (3) Mn(II), (4) Co(II),
5) Fe(III), (6) Ti(III), (7) Cu(II), (8) UO (VI), and (9) Cr(III).
2
(
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 4 2016

TRANSITION METAL CHELATES
905
Mn(II) and Co(II) possessed fairly good antibacterial
activity against E. coli. The Fe(III) and Zr(IV)
complexes showed good activity against S. typhias as
compared to the other complexes. The Ti(III) and
uranyl complexes showed the smaller zone of inhibit-
tion against P. aeruginosa. The Cu(II) and Zr(IV)
complexes exhibited enhanced activity towards
S. aureus.
water bath during 3–4 h. After cooling to ambient, the
orange-colored solid was filtered, washed with
methanol and diethyl ether, recrystallized from hot
1
DMF, and dried in vacuum. Yield 70%, mp 303°C. H
NMR spectrum, δ, ppm: 6.7–7.5 m (8H, H ), 10.4 s
Ar
(1H, NH, ring), 11.3 s (1H, NH), 12.14 s (1H, OH).
Synthesis of complexes. Equimolar amounts of the
corresponding metal salt and the ligand were dissolved
in a minimal volume of hot methanol and DMF,
respectively. The hot solutions were filtered and mixed
upon continuous stirring. The reaction mixture was
then digested on a sand bath.
In general, the results revealed that the ligand
antibacterial activity was enhanced after complexation
with the metal ions. According to the Tweedy’s
chelation theory [28], the chelation reduces the polarity
of the compound mainly owing to the partial sharing of
the metal positive charge with the donor groups as well
as possible π-electron density delocalization over the
aromatic ring [29, 30]. This increases the lipophilic
character of the metal chelate and favors its permeation
through the lipid layer of a bacterial membrane. Hence,
the enhancement of the ligand antibacterial activity
upon the chelation was assigned to the increased
lipophilic character of the complexes. As expected, the
toxicity was increased at higher concentration of the
complexes.
In the case of Zr(IV) complexes, zirconyl oxy-
chloride octahydrate (0.64 g, 0.002 mol) was dissolved
in methanol (15 mL), a methanolic solution of an-
hydrous sodium acetate (0.32 g, 0.004 ml in 15 mL)
was added, and the mixture was stirred during 5 min.
The precipitated sodium chloride was filtered off. The
ligand was dissolved in a minimal volume of hot
DMF; the solution containing oxozirconium(IV)
diacetate was added upon continuous stirring, and the
mixture was refluxed on a sand bath. The colored
precipitate was filtered off and washed sequentially
with methanol, DMF, and petroleum ether. The
product was dried in air at room temperature and
EXPERIMENTAL
stored in desiccators over CaCl . Yield 60–75%.
2
All the chemicals and solvents used were of analy-
tical grade. The metal salts [manganese(II) acetate
dihydrate, anhydrous ferric chloride, cobalt(II) acetate
dihydrate, nickel(II) acetate dihydrate, copper(II)
acetate dihydrate, titanium(IV) chloride, chromium(III)
chloride hexahydrate, zirconyl oxychloride octa-
hydrate, and uranyl acetate dihydrate] were commer-
cial products and were used as received.
Microanalysis of carbon, hydrogen, and nitrogen
content was performed using a Carlo Erba 1108 C-H-N-S
analyzer. Infrared spectra of the ligand and the
–1
complexes (4000–400 cm , KBr pellets) were
recorded using a Perkin-Elmer-RX-I spectrophoto-
1
meter. H NMR spectrum (a solution of the ligand in a
mixture of deuterated chloroform and DMSO) was
recorded using a Bruker DRX-300 NMR spectro-
photometer with TMS as internal reference. Magnetic
susceptibility of the metal complexes was measured
via the Gouy method at room temperature using
2-Hydroxy[2-oxo-1,2-dihydro-3H-indol-3-ylidene]-
benzohydrazide (L). A solution of 1H-indole-2,3-
dione (isatin) (2.94 g, 0.02 mol) in methanol (20 mL)
was added to a hot solution of salicylic hydrazide
(
3.04 g, 0.02 mol) in hot methanol (20 mL) upon
Hg[Co(SCN) ] as the reference. Thermogravimetric
4
stirring (Scheme 1). The mixture was heated using a
analysis was performed using a manually operated
Scheme 1.
O
O
O
O
N
H N
2
Reflux
.5 h
N
N
+
H
H
3
N
HO
N
O
HO
H
H
Isatin
Salicyl hydrazide
2-Hydroxy[2-oxo-1,2-dihydro-3H-indol-3-ylidene]-
benzohydrazide
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 4 2016

9
06
SURYAWANSHI et al.
thermobalance set up (specimen mass of 50–60 mg,
heating up to 700°C at 10 deg/min, air atmosphere;
copper(II) sulfate pentahydrate was measured under
the same conditions for calibration purpose). The solid
state d.c. electrical conductivity was measured as
function of temperature (ambient to 403 K) with a
micro voltmeter using the voltage drop method. The
antibacterial activity against E. coli, S. typhi, P.
aeruginosa, and S. aureus bacterial strains was
measured via the disc diffusion method [28]. Nutrient
agar and nutrient broth were used as the media. The
plates were inoculated with the 24 h cultures. The
compounds were tested at concentration of 500 ppm in
DMSO; the solutions prepared were soaked with
Whatmann filter paper no. 1 paper disc (10 mm in
diameter). The discs were incubated on the previously
seeded Petri dishes at 37°C during 24 h. The diameter
of the zone of inhibition was measured in millimeter.
DMSO was used as the blank.
10. Nag, J.K., Pal, S., and Sinha, C., Trans. Met. Chem.,
005, vol. 30, p. 523.
2
1
1
1
1
1
1
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