Synthesis of (2-hydroxo-5-chlorophenylaminoisonitrosoacetyl)phenyl ligands and their complexes: Spectral, thermal and solvent-extraction studies

Article abstract of DOI:10.1134/S0036023610040078

Four different types of new ligands Ar[COC(NOH)R] _n (Ar=biphenyl, n = 1 H₂L¹; Ar=biphenyl, n = 2 H ₄L²; Ar=diphenylmethane, n = 1 H₂L³; Ar=diphenylmethane, n = 2 H₄L⁴; R=2-amino-4-chlorophenol in all ligands) have been obtained from 1 equivalent of chloroketooximes Ar[COC(NOH)Cl] _n (HL¹-H₂L⁴) and 1 equivalent of 2-amino-4-chlorophenol (for H₂L¹ and H ₂L³) or 2 equivalent of 2-amino-4-chlorophenol (for H ₄L² and H₄L⁴). (Mononuclear or binuclear cobalt(II), nickel(II), copper(II) and zinc(II) complexes were synthesized with these ligands.) These compounds have been characterized by elemental analyses, AAS, infra-red spectra and magnetic susceptibility measurements. The ligands have been further characterized by ¹H NMR. The results suggest that the dinuclear complexes of H₂L¹ and H₂L³ have a metal:ligand ratio of 1:2; the mononuclear complexes of H₄L² and H₄L⁴ have a metal:ligand ratio of 1:1 and dinuclear complexes H₄L² and H₄L⁴ have a metal:ligand ratio of 2:1. The binding properties of the ligands towards selected transition metal ions (Mn ^II, Co^II, Ni^II, Cu^II, Zn ^II, Pb^II, Cd^II, Hg^II) have been established by extraction experiments. The ligands show strong binding ability towards mercury(II) ion. In addition, the thermal decomposition of some complexes is studied in nitrogen atmosphere.

Full text of DOI:10.1134/S0036023610040078

ISSN 0036ꢀ0236, Russian Journal of Inorganic Chemistry, 2010, Vol. 55, No. 4, pp. 530–540. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © Fatma Karipcin, Bülent Dede, Mustafa Cengiz, 2010, published in Zhurnal Neorganicheskoi Khimii, 2010, Vol. 55, No. 4, pp. 583–593.
COORDINATION COMPOUNDS
Synthesis of (2ꢀHydroxoꢀ5ꢀChlorophenylaminoisonitrosoacetyl)phenyl
Ligands and Their Complexes: Spectral, Thermal
and SolventꢀExtraction Studies1
Fatma Karipcin, Bülent Dede, and Mustafa Cengiz
Süleyman Demirel University, Faculty of Science and Arts, Department of Chemistry, 32260, IspartaꢀTurkey
eꢀmail: karipcin@fef.sdu.edu.tr
Received September 19, 2008
Abstract—Four different types of new ligands Ar[COC(NOH)R]n (Ar=biphenyl,
n
= 1 H2L1; Ar=biphenyl,
n
= 2 H4L2; Ar=diphenylmethane, = 1 H2L3; Ar=diphenylmethane, = 2 H4L4; R=2ꢀaminoꢀ4ꢀchloꢀ
n
n
rophenol in all ligands) have been obtained from 1 equivalent of chloroketooximes Ar[COC(NOH)Cl]n
(HL1–H2L4) and 1 equivalent of 2ꢀaminoꢀ4ꢀchlorophenol (for H2L1 and H2L3) or 2 equivalent of 2ꢀaminoꢀ
4ꢀchlorophenol (for H4L2 and H4L4). (Mononuclear or binuclear cobalt(II), nickel(II), copper(II) and
zinc(II) complexes were synthesized with these ligands.) These compounds have been characterized by eleꢀ
mental analyses, AAS, infraꢀred spectra and magnetic susceptibility measurements. The ligands have been
further characterized by 1H NMR. The results suggest that the dinuclear complexes of H2L1 and H2L3 have
a metal:ligand ratio of 1:2; the mononuclear complexes of H4L2 and H4L4 have a metal:ligand ratio of 1:1 and
dinuclear complexes H4L2 and H4L4 have a metal:ligand ratio of 2:1. The binding properties of the ligands
towards selected transition metal ions (MnII, CoII, NiII, CuII, ZnII, PbII, CdII, HgII) have been established by
extraction experiments. The ligands show strong binding ability towards mercury(II) ion. In addition, the
thermal decomposition of some complexes is studied in nitrogen atmosphere.
DOI: 10.1134/S0036023610040078
1
INTRODUCTION
the removal, separation and concentration of metallic
species, broadening its applications in the recycling of
resources in the field of metallurgy and waste water
treatment as demand increases for the development of
new approaches to resolve the various problems preꢀ
sented. Some metals such as CrIII,CoII, NiII, CuII, ZnII,
CdII, AgI, HgII, PbII, are recognized as highly toxic for
many biological systems [21, 22]. Thus, the determiꢀ
nation of trace amounts of these metals is becoming
increasingly important because of the increased interꢀ
est in environmental pollution. They are not degradꢀ
able, such metals can accumulate in the environment
and produce toxic effects in plants and animals even at
very low concentrations. Therefore, separation of
these trace metals is vital due to the potential health
and ecological hazard. There are many processes,
such as solvent extraction, ion exchange, adsorption
and complexing that can be used for the removal of
metals from wastewaters. For this purpose, many
oxime derivatives have been synthesized and their
extraction properties investigated by solvent extracꢀ
tion [23–27].
The chemistry of transition metal complexes with
ꢀdioxime ligands has been well studied and is the
α
subject of a lot of paper [1–7]. Yet little was known
about the coordination chemistry of ketooxime
ligands until last years, reports on these keto oxime
ligands are rather few [8–12]. Our interest in this area
evolved from previous studies of terdentate ligands and
a desire to prepare mono and binuclear complexes.
In recent years, the design and synthesis of binuꢀ
clear or polynuclear transition metal complexes has
gained sustained interest. Several types of ligand sysꢀ
tem, which can bind two metal ions in close proximity
have been used as biomimetic studies of binuclear
metalloenzyme and metalloproteins due to their inteꢀ
resting catalytic properties, their ability to stabilize
unusual oxidation states and possibilities for magnetic
interaction between two metal ions [13–16]. These
complexes have found many applications as catalysts
for specific purposes, as mimics for metallobiomoleꢀ
cules, and in investigations concerning the mutual
influence of two or more metal centers on the elecꢀ
tronic, magnetic and electrochemical properties of
such closely spaced metal centers [17–20].
In the previous studies, substituted 4,4'ꢀbis(alkylꢀ
aminoisonitrosoacetyl)diphenylmethanes [9] and
4ꢀ(alkylaminoisonitrosoacetyl)biphenyls and metal
chelates has been isolated [12]. These ligands have a
tendency to form a dimeric or polymeric complexes.
But the thermal characterization of the metal comꢀ
The new extractants with high selectivity for metal
ions are of interest for analytical purposes as well as for
1
The article is published in the original.
530

SYNTHESIS OF (2ꢀHYDROXOꢀ5ꢀCHLOROPHENYLAMINOISONITROSOACETYL)PHENYL
531
O
O
O
N OH
HO N
HO NH
N OH
(CH2)n
(CH2)n
NH OH
NH OH
Cl
= 1)
Cl
Cl
H4L2 (
n
= 0), H4L4 (
n = 1)
H2L1 ( = 0), H2L3 (
n n
1
4
Fig. 1. Structure of the ligands (H L –H L ).
2
4
plexes and solventꢀextraction studies of these kind of METU (AnkaraꢀTurkey). Melting points were meaꢀ
ligands, have not been reported earlier. In this study, as sured on a IA 9100 Electrothermal apparatus.
part of a systematic study, we describe the synthesis,
spectroscopic properties, solventꢀextraction studies
Preparation of the Ligands
and thermal decompositions of four new (alkylaminoꢀ
isonitrosoacetyl)phenyl ligands using same amine
(2ꢀaminoꢀ4ꢀchlorophenol) (Fig. 1) and their the
mononuclear and binuclear Co(II), Ni(II), Cu(II)
and Zn(II) complexes.
All ligands were prepared by a similar methods.
First, chloroketooximes (10 mmol, 2.60 g HL1, 3.65
g
H2L2, 2.74 HL3, 3.79 H2L4) were dissolved in EtOH
g g
(
40 cm3) and the mixture was cooled—
5°C. Then
2ꢀaminoꢀ4ꢀchlorophenol (11 mmol, 1.58 g for HL1
and HL3; 22 mmol, 3.16 g for H2L2 and H2L4) and Et3N
(10 mmol, 1.38 cm3 for HL1 and HL3; 20 mmol,
EXPERIMENTAL
Materials and Methods
2.77 cm3 for H2L2 and H2L4) and in MeOH (20 cm3
)
were added dropwise to solutions of chloroketooximes
over 15 min with cooling. Precipitation and colour
change were observed in the reaction medium immeꢀ
diately. After that period, the reaction mixture was
stirred 2 h at the same temperature. Then it was
allowed to stir at ambient temperature for 2 h. The
powder (resulted) from the reaction is insoluble in ethꢀ
anol and this was filtered off, washed aqueous sodium
bicarbonate (1%), distilled water, ethanol and dried on
All solvents, 2ꢀaminoꢀ4ꢀchlorophenol and metal
salts [Co(AcO)2
H2O, Zn(AcO)2
⋅
⋅
4H2O, Ni(AcO)2
2H2O] used for the synthesis and
⋅ 4H2O, Cu(AcO)2 ⋅
physical measurements were of reagent grade and used
as received. The starting materials (chloroketones)
were prepared by the FriedelꢀCrafts acylation reaction
of biphenyl and diphenylmethane with chloroacetyl
chloride in 1 : 1 and 1 : 2 molar ratio according to litꢀ
erature procedures [28–30]. Chloroketooximes [30,
31] were also prepared by following the literature methods.
P2O5
.
Elemental analyses of the ligands and their comꢀ
plexes were obtained on a LECO 932 CHNS analyzer.
1H NMR spectra of the ligands were obtained by the
Laboratories of the Scientific and Technical Research
Council of Turkey (TUBITAK) using TMS as the
internal reference in CDCl3 or deuterated DMSO.
1H NMR spectra of the complexes could not be deterꢀ
mined, since these compounds are not totally soluble
in organic solvents. Infrared spectra were recorded as
KBr pellet on a Shimadzu IRPrestigeꢀ21 FTꢀIR Specꢀ
trophotometer in the range 4000–400 cm–1. Atomic
absorption spectrophotometer used to determine
metal ion concentration in the aqueous phase was Perꢀ
kin Elmer 800 AAS. The spectrophotometric meaꢀ
surements were carried out with a Perkin Elmer
Preparation of Metal Complexes
All complexes were prepared by similar methods. A
solution of equivalent amount of metal salt in ethanol
(
20 cm3) was added to a hot solution of ligand (H2L1–
H4L4) [1 mmol, 0.367 g H2L1 0.579
g g
H4L2, 0.381
H2L3, 0.593
g
H4L4] in ethanol,(50 cm3) and was conꢀ
tinuously stirred. A distinct change in colour and
decrease in pH (pH = 3.0–3.5) was observed, an
equivalent amount of ethanolic solution of KOH
(0.1 M) was added dropwise to adjust a pH value of
about 5–6, solid product precipitated. The complex
precipitated, was kept on a water bath at 80oC for one
hour in order to complete the precipitation. The mixꢀ
ture was cooled to ambient temperature and the solid
product was filtered off. Then it was washed hot water,
λ
20 U.v.ꢀvis. Spectrometer. Magnetic properties were
determined by means of a Sherwood Scientific MX1
Model Gouy Magnetic Susceptibility Balance. The
thermogravimetric analysis (TG and DTG) was carried
ethanol and dried on P2O5
.
The colours, yield, melting points, elemental analꢀ
out in dynamic nitrogen atmosphere (20 mL min–1) with yses and IR data of complexes and ligands are given in
a heating rate of 10oC min–1 using a Perkin Elmer Pyris Table 1 and 3. H NMR data of ligands are given in
1
1 TGA thermal analyzer in the Central Laboratory at Table 2.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 4 2010

532
KARIPCIN et al.
Solvent Extraction
blank experiment, no metal ion picrate extraction was
detected. The extractability was calculated by using
the equation below:
The extraction properties of the Schiff base ligands
(
H2L1, H4L2, H2L3 and H4L4) were investigated under
liquid–liquid phase and neutral conditions using
Extractability(%) = [(A0 – A) /A0]
the absorbance in the absence of ligand. A denotes the
× 100 where A0 is
selected metal picrates (MnII, CoII, NiII, CuII, ZnII,
PbII, CdII, HgII) as substrates and measuring by U.v.ꢀ absorbance in the aqueous phase after extraction.
vis. measurements the amounts of metal picrate in the
aqueous phase before and after treatment with the
compounds. About 10 cm3 of
2 ×
10–5 M aqueous
RESULTS AND DISCUSSION
picrate solution and 10 cm3 of
1
×
10–3 M solution of
Chloro ketones (1) were prepared from chloroꢀ
acetyl chloride with biphenyl and diphenylmethane in
presence of aluminium chloride according to Friedelꢀ
Crafts acylation [28–30]. Chloro ketooximes (2) were
obtained from the reaction of (1) with alkyl nitrite in
presence of dry HCl gase [30, 31]. 4 and 4,4'ꢀ(2ꢀ
hydroxoꢀ5ꢀchlorophenylaminoisonitrosoacetyl)pheꢀ
nyl ligands (H2L1–H4L4) were prepared by a condenꢀ
sation reaction of (2) with 2ꢀaminoꢀ4ꢀchlorophenol
(Scheme 1). 4ꢀ(2ꢀhydroxoꢀ5ꢀchlorophenylaminoꢀ
isonitrosoacetyl)biphenyl [H2L1], 4,4'ꢀ(2ꢀhydroxoꢀ5ꢀ
chlorophenylaminoisonitrosoacetyl)biphenyl [H4L2],
ligand in CHCl3 were vigorously agitated in a stopꢀ
pered plastic tube with a mechanical shaker for 2 min,
then magnetically stirred at 25°C for 1 h, and finally
left standing for an additional 30 min. The concentraꢀ
tion of the picrate ion remaining in the aqueous phase
was then determined spectrophotometrically. Blank
experiments showed that no picrate extraction
occurred in the absence of ligand. Metal picrates were
prepared by successive addition of a
nitrate solution to
10–5 M aqueous picric acid soluꢀ
tion and shaken at 25 for 1 h. These metal picrates
MnII, CoII, NiII, CuII, ZnII, PbII, CdII, HgII) were meaꢀ
1 ×
10–2 M metal
2
×
°C
(
4
ꢀ(2ꢀhydroxoꢀ5ꢀchlorophenylaminoisonitrosoacetyl)diꢀ
phenylmethane [H2L3], and 4,4'ꢀ(2ꢀhydroxoꢀ5ꢀchloꢀ
rophenylaminoisonitrosoacetyl)diphenylmethane [H4L4
sured by U.v.ꢀvis. using maximum wavelength 352 nm.
For each combination of host and metal picrate, the
picrate extraction was conducted on three different
samples and the average value of percent picrate
]
were prepared. Analytical and spectroscopic data of
the ligands (H2L1–H4L4) clearly confirmed the sucꢀ
extracted, was calculated. In the absence of host, a cess of the condensation reaction.
Ar[COC(NOH)Cl]n +
xRNH2
Ar[COC(NOH)NHR]n +
xHCl
Ar = biphenyl, n = 1,
x
= 1 H2L1
Ar = biphenyl,
n = 2, x
=2 H4L2
Ar = diphenylmethane, = 1,
n
x
RNH2 = 2ꢀaminoꢀ4ꢀchlorophenol
= 1 H2L3
Ar = diphenylmethane,
n
= 2,
x
= 2 H4L4
1
4
Scheme. Synthesis of (alkylaminophenylisonitrosoacetyl)phenyles ( H L –H L ).
2
4
The mononuclear or binuclear metal complexes to –NH– protons at
δ= 7.85–8.13 ppm, appeared
formed between these ligands and metal salts. The after the condensation reaction. The aromatic C–H
structural formula of the ketooxime ligands and their protons of the ligands measured at 6.77–7.78 ppm,
complexes was verified by elemental analyses, aliphatic C–H protons at 3.70–4.20 ppm, OH proꢀ
1H NMR, IR spectral data and elemental analyses tons phenol groups 6.61–6.81 ppm, respectively.
data. Analytical results of the ligands and their comꢀ These values are in accord with the previously reported
plexes are listed in Table 1. All compounds were found oxime derivatives [4–9, 32, 33].
to be nonhygroscopic and stable in air.
FTꢀIR Spectra
1HNMR Spectra
The FTꢀIR spectra of chloroketooximes, the
The 1H NMR shifts are listed and assigned in Table ligands and their complexes provide an insight into the
2. The 1H NMR spectra of chloroketooximes exhibit a mode of bonding of the ligand to the metal ions.
singlet peak for the OH protons of oxime group at Assignments were made based on typical group freꢀ
9.85–13.69 ppm range. In all ligands, a singlet peak in quencies. The most important IR spectral bands of the
9.74–11.09 ppm range is also attributed to the OH ligands and their complexes are listed in Table 3. In the
proton of the oxime group. The lower shift of the OH IR spectrum of these compounds, the difference
protons of the oxime group is typical of condensation between the spectra of chloroketooximes (HL1–H2L4
)
reaction with 4ꢀbiphenylhydroximoyl chloride and and the ligands (H2L1–H4L4) is clear by the presence
corresponding amines. The chemical shifts belonging of characteristic vibrations, at 3420–3319 cm–1
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 4 2010

SYNTHESIS OF (2ꢀHYDROXOꢀ5ꢀCHLOROPHENYLAMINOISONITROSOACETYL)PHENYL
533
Table 1. Analytical and physical data for the ligands and their complexes
Calcd. (Found) %
μ
(B.M.)
Yield
(%)
eff
Compound
Colour
Light yellow
Light brown
Brown
Mp (°C)
per M(II)
C
H
N
Metal
HL1
–
169
162
284
54
65
77
83
43
63
35
56
79
90
75
69
79
75
70
46
97
65
76
94
78
65
83
42
64.75
(64.72)
65.49
(65.39)
52.25
(52.07)
52.28
(51.94)
51.73
(51.54)
50.55
(51.01)
52.63
(52.12)
58.04
(58.12)
43.94
(43.61)
43.97
(43.74)
51.04
(51.12)
41.41
(41.69)
65.82
(65.34)
66.23
(66.08)
53.24
(52.05)
53.26
(52.95)
52.72
(52.58)
52.52
(52.27)
53.85
(54.20)
58.70
(58.81)
50.75
(50.40)
44.72
(44.45)
50.41
(50.75)
43.97
3.88
(4.05)
4.12
5.39
(4.96)
7.64
–
(C14H10NO2Cl)
H2L1
–
–
(3.97)
3.73
(7.58)
6.09
(C20H15N2O3Cl)
[Co2(L1)2(H2O)2]
⋅
2H2O
2.73
3.17
1.22
Dia.
–
12.82
(C40H34N4O10Cl2Co2)
[Ni2(L1)2(H2O)2]
2H2O
(C40H34N4O10Cl2Ni2)
[Cu2(L1)2(H2O)2]
2H2O
(C40H34N4O10Cl2Cu2)
[Zn2(L1)2(H2O)4]
H2O
(3.64)
3.73
(3.88)
3.69
(3.46)
3.82
(3.42)
2.76
(5.86) (12.60)
6.10 12.77
(5.67) (12.54)
6.03 13.68
(5.82) (13.27)
5.89 13.76
(5.78) (13.47)
7.67
(6.61)
9.67
⋅
Dark brown
Dark brown
Brown
>300
240
⋅
⋅
255
(C40H36N4O11Cl2Zn2)
H2L2
(C16H10N2O4Cl2)
H4L2
Yellow
169
–
(4.74)
3.48
–
Light brown
205*
–
(C28H20N4O6Cl2)
(3.91)
3.16
(9.87)
7.32
[Co(H2L2)]
⋅
2H2O
(C28H24N4O10Cl2Co2)
[Ni2(L2)(H2O)2]
2H2O
(C28H24N4O10Cl2Ni2)
[Cu(H2L2)]
H2O
(C28H20N4O7Cl2Cu)
[Zn2(L2)(H2O)2]
2H2O
3.76
3.35
1.43
Dia.
–
Dark brown >300
15.40
(3.48)
3.16
(3.52)
3.06
(3.41)
3.23
(7.67) (15.61)
7.33 15.35
(7.16) (15.46)
8.50
(8.29)
6.90
⋅
Dark green
Dark brown
Brown
235
222
⋅
9.64
(9.59)
16.10
⋅
>300
108
(C28H26N4O12Cl2Zn2)
HL3
[C15H12NO2Cl]
H2L3
(3.61)
4.42
(4.18)
4.50
(6.86) (19.21)
Yellow
5.12
(4.99)
7.36
–
–
Light brown
165
–
(C21H17N2O3Cl)
(4.36)
4.04
(7.19)
5.91
[Co2(L3)2(H2O)2]
⋅
2H2O
(C42H38N4O10Cl2Co2)
[Ni2(L3)2(H2O)2]
2H2O
(C42H38N4O10Cl2Ni2)
[Cu2(L3)2(H2O)2]
2H2O
(C42H38N4O10Cl2Cu2)
[Zn2(L3)2(H2O)2]
2H2O
2.78
3.12
1.24
Dia.
–
Dark brown >300
12.44
(3.83)
4.04
(3.93)
4.00
(3.66)
3.99
(3.73)
3.19
(5.67) (12.69)
5.92 12.39
(5.72) (12.65)
5.86 13.28
(5.63) (13.63)
5.83 13.62
(5.75) (13.32)
7.39
(7.00)
9.44
⋅
Dark brown
Dark green
Brown
282
⋅
215
⋅
255
(C42H38N4O10Cl2Zn2)
H2L4
(C17H12N2O4Cl2)
H4L4
Cream
171–172
205
–
(3.30)
3.74
–
Light brown
Brown
–
(C29H22N4O6Cl2)
(4.21)
3.52
(9.86)
8.16
[Co(H2L4)]
⋅
2H2O
(C29H24N4O8Cl2Co)
[Ni2(L4)(H2O)2]
2H2O
(C29H26N4O10Cl2Ni2)
[Cu(H2L4)]
2H2O
(C29H24N4O8Cl2Cu)
[Zn2(L4)(H2O)2]
2H2O
3.52
2.82
1.47
Dia.
230
8.59
(8.16)
15.07
(3.83)
3.36
(8.24)
7.19
⋅
Green
187
(3.88)
3.50
(3.69)
3.31
(7.47) (15.31)
⋅
Green
279
8.11
(8.03)
7.07
9.20
(9.06)
16.51
⋅
Yellow
250
(C29H26N4O10Cl2Zn2)
* Decomposition point
(43.61)
(3.78)
(7.34) (16.80)
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 4 2010

534
KARIPCIN et al.
1
Table 2. The H NMR data ( as p.p.m.) for chloroketooximes and the ligands
Compound
HL1
O–Ha
O–Hb
C–H(arom.)
C–H(aliph.)
N–H
13.69 (s,1H)
11.09 (s, 1H)
11.55 (s, 2H)
10.13 (s, 2H)
9.85 (s, 1H)
9.74 (s, 1H)
13.20 (s, 2H)
10.40 (s, 2H)
–
6.68 (s, 1H)
–
7.31–8.08 (m, 9H)
7.01–7.78(m, 12H)
6.90–7.75 (m, 8H)
7.20–7.69(m, 14H)
8.10–7.10 (m, 9H)
6.82–7.54(m, 12H)
6.90–7.40 (d, 8H)
–
–
8.06 (s, 1H)
–
[9]
H2L1
–
H2L2
H4L2
HL3
–
6.81(s, 2H)
–
–
7.85(s, 2H)
–
4.20 (s, 2H)
4.06 (s, 2H)
3.70 (s, 2H)
H2L3
H2L4
H4L4
6.74 (s, 1H)
–
8.13 (s, 1H)
–
[5]
6.61 (s, 2H)
6.77–7.59 (m, 14H) 3.89 (s, 1H)
7.89 (s, 2H)
s – singlet, d – dublet, t – triplet, m – multiplet: a – oxime, b – phenol.
belonging to the NH groups. The ligands exhibit two amount of KOH (0.1 M) in ethanol gave the desired
OH stretching frequencies (oxime, 3311–3271 cm–1 complexes in 42–97% yields. The room temperature
and phenolic OH, 3524–3493 cm–1) and NO (1011–
990 cm–1) as for substituted aminooximes.
magnetic moment measurements show that all Zn(II)
complexes are diamagnetic. The nickel(II) complexes
are paramagnetic with magnetic susceptibility values
of 2.82–3.35, which fit the d8 metal ion in an octaheꢀ
dral or square pyramidal structure, the twoꢀspin value,
2.83 B.M. [37]. The copper(II) and cobalt(II) comꢀ
plexes are paramagnetic with magnetic susceptibilities
1.22–1.47 and 2.73–3.76, respectively. The CuII comꢀ
plexes fits the a spin value 1.73 B.M. and CoII comꢀ
The IR spectra of all the metal complexes resemble
each other. The spectra of the complexes, hydroxyl
frequencies of phenol and oxime groups are shifted to
higher or lower frequencies, which indicates the sepaꢀ
ration of OH protons of both phenol and oxime
groups. The free OH vibration of phenol appears at
3524–3493 cm–1 range in the ligands and disappears
completely in the binuclear and mononuclear metal plexes fits triꢀspin value 3.87 B.M., which are consisꢀ
complexes. This result indicates coordination through tent with a weak field octahedral or square pyramidal
the Oꢀatoms of the phenolates in mononuclear metal geometry as expected. The magnetic moments of the
complexes of H4L2 and H4L4 [9].
dinuclear copper(II) complexes lie in the 1.22 and
1.24 B.M., which is well below the spinꢀonly value of
1.73 B.M., indicating spinꢀexchange interaction
between copper(II) ions. The magnetic moments of
the dinuclear cobalt(II) complexes is 2.78 and
2.73 B.M., which is also below the three spin value of
3.87 B.M. And magnetic moments of the dinuclear
NiII complexes are below the two spin value of
2.83 B.M. Reported some bridged NiII and CoII comꢀ
plexes, exhibit moderate to weak antiferromagnetic
Because νOH stretching vibrations of the complexes
appeared in the range of 3502–3435 cm–1 are belongꢀ
ing to crystal water molecules of the complexes. The
coordinated water appears at frequencies lower than
those of the crystal water [34, 35]. Therefore, OH
stretching vibrations of oxime groups in mononuclear
complexes of H4L2 and H4L4 and coordine H2O in the
complexes also are probably shown same range with
NH stretching vibrations [12]. In the complexes,
N⎯H stretching vibrations are shifted to higher or interactions [6, 12, 38, 39].
lower frequencies in the 3397–3361 cm–1 range, and
this confirms that the nitrogen atom of the amine
group is coordinated to the metal ions. The coordinaꢀ
tion of the amine nitrogen to the metal ion can be
inferred from the shift of vC=N from 1607–1606 to
about 1605–1576 cm–1. Strong absorption bands in
the range of 1674–1640 cm–1 characterize the C=O
group of the ligands in the complexes. Metal comꢀ
plexes show the characteristic bands at 998–923 cm–1
belong to N–O stretching vibrations. FTꢀIR data of
the ligands and their complexes are in good agreement
with those of known oximes [4–9, 36].
Extraction Ability of the Ligands
The extraction efficiencies of the ligands toward
metal ions (MnII, CoII, NiII, CuII, ZnII, PbII, CdII, HgII
)
were determined by the picrate extraction method
developed by Pedersen [40]. Solvent extraction of
aqueous metal cation into water saturated organic
hosts' solutions, were performed at 25°C. An aqueous
solution containing metal picrate was extracted with
the host solution (CHCl3), and the data are expressed
as percentages of the cation extracted (E%) by the
In order to prepare complexes, we used a standard
procedure through the reaction of ligands with metal ligand, as given in the Table 4 and represented in
salts. A mixture of ligand, metal salts and an equivalent Fig. 5.
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SYNTHESIS OF (2ꢀHYDROXOꢀ5ꢀCHLOROPHENYLAMINOISONITROSOACETYL)PHENYL
535
1
Table 3. IR spectral data for the ligands and their metal complexes (cm–
)
Compound
N–H
ν(OH)
C=O
ν
(C=N)
ν(NO)
HL1
H2L1
–
3256 b
1655 s
1602 s
1029 s
990 m
3420 m
3493 s
3275 b
1691 m
1607 m
[Co2(L1)2(H2O)2]
[Ni2(L1)2(H2O)2]
[Cu2(L1)2(H2O)2]
[Zn2(L1)2(H2O)4]
H2L2
⋅
2H2O
2H2O
2H2O
H2O
3382 b
3391 b
3371 b
3377 b
–
3458 b
3461 b
3447 b
3469 b
3283 b
3524 s
3311 b
3448 b
3495 b
3487 b
3502 b
3229 b
3496 s
3294 b
3436 b
3435 b
3435 b
3487 b
3270 b
3518 s
3271 b
3439
1653 m
1667 m
1640 m
1661 m
1657 s
1602 s
1598 s
1576 s
1582 m
1607 m
1607 s
931 m
923 m
948 m
931 m
1036 s
1011 m
⋅
⋅
⋅
H4L2
3381 b
1667 s
[Co(H2L2)]
[Ni2(L2)(H2O)2]
[Cu(H2L2)]
H2O
⋅
2H2O
3393 b
3392 b
3397 b
3361 b
–
1652 s
1652 s
1663 s
1674 s
1655 s
1682 m
1603 s
1602 s
1601 m
1602 s
1598 s
1607 m
945 m
938 m
998 m
944 m
1027 s
990 m
⋅
2H2O
⋅
[Zn2(L2)(H2O)2]
HL3
⋅
2H2O
H2L3
3319 m
[Co2(L3)2(H2O)2]
[Ni2(L3)2(H2O)2]
[Cu2(L3)2(H2O)2]
[Zn2(L3)2(H2O)2]
H2L4
⋅
2H2O
2H2O
2H2O
2H2O
3368 b
3372 b
3364 b
3369 b
3326 w
3319 b
1646 m
1653 m
1647 m
1654 m
1670 s
1602 s
1600 s
1583 s
1603 m
1602 s
1606 s
932 m
926 m
948 m
930 m
1017 w
1010 m
⋅
⋅
⋅
H4L4
1654 s
[Co(H2L4)]
[Ni2(L4)(H2O)2]
[Cu(H2L4)]
2H2O
[Zn2(L4)(H2O)2]
2H2O
⋅
2H2O
2H2O
3363 b
3364 b
3375 b
3364 b
1652 s
1661 s
1663 s
1652 s
1605 s
1602 m
1605 s
1604 m
943 m
943 m
953 m
943 m
⋅
3469 b
3439 b
3496 b
⋅
⋅
s: strong, m: medium, w: weak, b: broad.
Hostꢀguest interactions between macrocyclic ligands from H2L1 and H2L3 to H4L2 and H4L4
ligand and metal cation are interesting for analytical increases. This increase is effective in the extraction
processes. The cation binding properties of the ligands levels of some metal ions such as PbII and CuII, but it is
depend upon different factors such as macrocyclic not effective for all metal ions (especially HgII and ZnII
effect, cavity size, the hard and soft acids and bases ions). Our ligands contain soft donor nitrogen atoms
(HSAB) principles and the type and number of donor [24–26]. Therefore they show a very clear preference
atoms. The extraction ability of the ligands in this for HgII. While the extraction levels for the soft Lewis
study varies as HgII > PbII ӷ CuII > NiII > ZnII = CoII > acid, HgII (82.34–87.36%) are very superior to ours,
CdII > MnII. However ionic radius of these metal ions for PbII (58.13–79.52%) are second, and mainly for
varied as PbII > HgII > CdII > MnII > CuII > ZnII > CoII > CuII (36.85–41.49%) are inferior. It is clear from these
NiII [41]. These results suggest that the match between data that the complexation ability of the ligands
the cation and the ligands cavity dimensions is not an toward HgII is much higher and all ligands are excelꢀ
evident factor in selectivity. The type of donor atoms in lent extractants for HgII ion. Also the presence of
all ligands of this study is same. But the type of aroꢀ oxime groups (–C=ON–OH) indicate that the oxime
matic group bonding carboyl group and the number of groups play an important role in the extraction process
donor atoms in the ligands are changing. The type of [42]. It is difficult to comment whether or not the
aromatic group in the ligand is not an important factor increase in extraction capability is the result of oxime
in selectivity. The number of donor atoms in the groups or the increase in the number of donor atoms,
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 4 2010

536
KARIPCIN et al.
Table 4. Extraction of metal picrates with ligandsa
Percent of metal picrate extracted (%)b
Ligand
H2L1
H4L2
H2L3
H4L4
Mn2+
Co2+
Ni2+
Cu2+
Zn2+
Pb2+
Cd2+
Hg2+
4.47
7.51
3.26
6.61
14.22
15.76
11.26
15.84
19.71
23.42
16.24
38.14
41.49
36.85
39.94
16.34
15.96
17.82
13.48
70.14
79.52
58.13
62.89
6.63
9.12
6.29
8.81
87.36
85.60
82.34
84.57
20.13
a
–5
–3
–2
H O/CHCl = 10/10 (v/v): [picric acid] = 2 × 10 M, [ligand] = 1 × 10 M, [metal nitrate] = 1 × 10 M, 298 K, 1 h contact time.
Average for three independent measurements.
2
3
b
but, according to these data, we can conclude that, the accounted for the loss of two biphenyls and two CO
hard and soft acids and bases principles and the numꢀ groups. The remaining step of decompositions occur
ber of donor atoms are much more effective than the within the temperature range 580–1000
°C with an
other factors [43, 44]. estimated mass loss of 29.50% (calculated mass loss =
28.74%) which corresponds to the decomposition of
the compound completely leaving CoO residue.
Thermal Analyses
The NiII complex, [Ni2(L1)2(H2O)2]
⋅
2H2O, is therꢀ
The TG for the some metal complexes of these mally decomposed in five successive decomposition
ligands was carried out within the temperature range steps within the temperature range 40–1000
. In the
from room temperature up to 1000 . Thermal data of first step, estimated mass loss of 8.10% (calculated
the complexes are given in Table 5. The correlations mass loss = 7.84%) within the temperature range 40–
between the different decomposition steps of the comꢀ 190
can be attributed to the liberation of two moles
°C
°C
°C
plexes with the corresponding weight losses are disꢀ of coordinated water and two moles of crystallization
cussed in terms of the proposed formulae of the comꢀ water. Other three decomposition steps of estimated
plexes.
The CoII complex with the general formula
[Co2(L1)2(H2O)2]
2H2O is thermally decomposed in
six successive decomposition steps. First step occurs
within the temperature range 30–130 with an estiꢀ
mass loss 46.80% which is responsibly accounted for
loss of two biphenyl two Cl and two CO groups (calcuꢀ
lated mass loss = 47.15%) within the temperature
⋅
range 190–650
1000 , therefore we did not determine metallic resiꢀ
due.
The CuII complex with the general formula
2H2O was thermally decomposed in
may five successive decomposition steps. In the first step,
be attributed to the loss of two H2O and 2 Cl molecules estimated mass loss of 8.00% (calculated mass loss =
(calculated mass loss = 11.63%). The third, forth and 7.76%) within the temperature range 50–240 can be
fifth steps occur within the same temperature range attributed to the liberation of four H2O molecule. The
305–580 with an estimated mass loss 38.90% (calꢀ second decomposition step occurs within the temperꢀ
culated mass loss = 39.41%), which is reasonably ature range 240–295
°C. Decomposition is going on in
°C
°C
mated mass loss 3.60% (calculated mass loss = 3.92%)
are reasonably accounted for the liberation of the two
H2O molecules. The second estimated mass loss of [Cu2(L1)2(H2O)2]
⋅
11.30% within the temperature range 130–305°C
°C
°C
°C
with an estimated mass loss
Cl
O2H
O
NH
O
O
O
X
N
(CH2)n
M
X
M
(CH2)n
N
O
H2O
NH
O
Cl
1
3
II
II
II
II
Fig. 2. Dinuclear metal complexes of H L and H L (M = Co , Ni , Cu and Zn ; X: H O or O).
2
2
2
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 4 2010

SYNTHESIS OF (2ꢀHYDROXOꢀ5ꢀCHLOROPHENYLAMINOISONITROSOACETYL)PHENYL
Cl
537
O
H
O
NH
(CH2)n
N O
M
O
O N
H
NH
Cl
n
II
II
2
4
Fig. 3. Mononuclear Co and Cu complexes of H L and H L
.
4
4
N
O2H
M
O
HN
O
O
O
Cl
M
Cl
NH
H2O
N
(CH2)n
O
n
II
II
2
4
Fig. 4. Dinuclear Ni and Zn complexes of H L and H L
.
4
4
7.20% (calculated mass loss = 7.64%), which is reaꢀ of six stages. The first step with estimated mass loss of
sonably accounted for the loss of two Cl atoms.
Decomposition was going on in 1000 , therefore we
did not determine metallic residue.
1.95%, found within the temperature range 50–105°C.
°
C
Corresponding to loss of one H2O molecule (calcuꢀ
lated mass loss = 1.90%). The second step with an estiꢀ
mated mass loss 7.45% which is due to loss of four H2O
The ZnII complex, with the general formula
[Zn2(L1)2(H2O)4]
⋅
H2O, shows decomposition pattern molecules within the temperature range 105–275°C
100
90
80
70
60
50
40
30
20
10
0
1
2
3
4
Mn2+ Co2+ Ni2+ Cu2+ Zn2+
Pb2+ Cd2+ Hg2+
1
2
3
4
Fig. 5. Extraction percentage of the metal picrates with ligands. Ligands: 1 = H L , 2 = H L , 3 = H L , 4 = H L H O/CHCl =
2 4 2 4 2 3
ꢀ5
–3
–2
10/10 (v/v): [picric acid] =
2 × 10 M, [ligand] = 1 × 10 M, [metal nitrate] = 1 × 10 M, 298 K, 1 h contact time.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 4 2010

538
KARIPCIN et al.
Table 5. Thermoanalytical results (TG, DTG) of metal complexes
Estimated (%, calculated)
TG range
DTGmax
Metalliꢀ
cresidue
Complex
Assignment
(°C)
(°C)
Mass loss
Total mass loss
[Co2(L1)2(H2O)2]
⋅
2H2O
30–130
70
3.60 (3.92)
Loss of two H2O molecules
130–305 290
11.30 (11.63)
Loss of two H2O and 2 Cl
molecules
305–580 365, 445, 525 38.90 (39.41)
Loss of 2 biphenyl and 2 CO
groups
580–1000 710
29.50 (28.74) 83.30 (83.70) Decomposition of the comꢀ 2 CoO
pound completely
[Ni2(L1)2(H2O)2]
⋅
2H2O
40–190
75
8.10 (7.84)
Loss of four H2O molecules
190–650 335, 430, 575 46.80 (47.15)
Loss of 2 biphenyl 2 Cl and 2
CO groups
650–1000 730
–
Decomposition is going on
Loss of four H2O molecules
Loss of two Cl atoms
?
?
[Cu2(L1)2(H2O)2]
[Zn2(L1)2(H2O)4]
⋅
⋅
2H2O
H2O
50–240 230
8.00 (7.76)
7.20 (7.64)
240–295 255
295–1000 340, 710, 755
Decomposition is going on
Loss of one H2O molecule
Loss of four H2O molecules
Loss of two Cl atoms
50–105
80
1.95 (1.90)
7.45 (7.58)
7.30 (7.46)
38.40 (38.13)
105–275 245
275–330 305
330–515 430
Loss of 2 biphenyl and 2 CO
groups
515–725 575, 630
27.35 (27.80) 82.45 (82.87) Decomposition of the comꢀ 2 ZnO
pound completely
[Ni2(L2)(H2O)2]
⋅
2H2O
30–190
87
9.80 (9.42)
Loss of four H2O molecule
190–487 230, 434
36.40 (36.50)
Loss of biphenyl 2 Cl and 2
CO groups
487–740 637
34.70(34.55) 80.90 (80.47) Decomposition of the comꢀ 2 NiO
pound completely
[Cu(H2L2)]
[Co(H2L4)]
⋅
⋅
H2O
40–150
95
3.10 (2.73)
Loss of one H2O molecule
150–245 215
42.45 (42.36)
Loss of biphenyl 2 Cl and 2
CO groups
580–980 765, 855
45.10 (45.27) 90.65 (90.36) Decomposition of the comꢀ Cu
pound completely
2H2O
30–105
65
5.50 (5.26)
Loss of two H2O molecules
105–490 220, 445
45.50 (45.21)
Loss of diphenylmethane 2
Cl and 2 CO groups
490–920 570, 900
38.50 (38.58) 89.50 (89.05) Decomposition of the comꢀ CoO
pound completely
[Ni2(L4)(H2O)2]
⋅
2H2O
30–110
75
5.10 (4.63)
4.70 (4.63)
Loss of two H2O molecules
110–200 180
200–460 425
460–625 550
Loss of other two H2O moleꢀ
cules
37.40 (37.64)
Loss of diphenylmethane 2
Cl and 2 CO groups
38.30 (38.60) 85.50 (84.93) Decomposition of the comꢀ 2 Ni
pound completely
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 55 No. 4 2010

SYNTHESIS OF (2ꢀHYDROXOꢀ5ꢀCHLOROPHENYLAMINOISONITROSOACETYL)PHENYL
539
(calculated mass loss = 7.58%). The third estimated 200
mass loss of 7.30% (calculated mass loss = 7.46%) mated mass loss of 37.40% (calculated mass loss =
within the temperature range 275–330 can be 37.64%) within the temperature range 200–460 can
attributed to the liberation of two Cl atoms. The forth be attributed to the liberation of diphenylmethane,
step occurs within the temperature range 330–515 two Cl and two CO groups. The last step occurs within
and fifth and sixth steps occur within the temperature the temperature range 460–625 with an estimated
range 515–725 with an estimated total mass loss total mass loss 38.30% (calculated total mass loss =
°C (calculated mass loss = 4.63%). The third estiꢀ
°C
°C
°C
°C
°C
82.45% (calculated total mass loss = 82.87%), which is 38.60%), which is reasonably accounted for decompoꢀ
reasonably accounted for decomposition of the comꢀ sition of the compound completely leaving Ni as resiꢀ
pound completely leaving ZnO as residue.
due.
The NiII complex with the general formula
[Ni2(L2)(H2O)2]
⋅ 2H2O was thermally decomposed in
CONCLUSIONS
four successive decomposition steps. The first estiꢀ
mated mass loss of 9.80% within the temperature
range 30–190°C may be attributed to the liberation of
four H2O molecule (calculated mass loss = 9.42%).
The remaining steps of decomposition occur within
(2ꢀHydroxoꢀ5ꢀchlorophenylaminoisonitrosoꢀ
acetyl)phenyl ligands (H2L1–H4L4) and their monoꢀ
and dinuclear cobalt(II), nickel(II), copper(II) and
zinc(II) complexes were synthesized and characterꢀ
ized by elemental analyses, magnetic susceptibility
the temperature range 190–487°C (loss of biphenyl,
1
measurements, IR and H NMR. It was found that,
two Cl and two CO groups) and 487–740 with an estiꢀ
mated total mass loss of 80.90% (calculated mass loss =
80.47%) which corresponds to decomposition of the
compound completely leaving NiO residue.
the dinuclear complexes of H2L1 and H2L3 have a
metal : ligand ratio of 1 : 2 (Fig. 2); the mononuclear
complexes of H4L2 and H4L4 have a metal : ligand ratio
of 1 : 1 (Fig. 3) and dinuclear complexes H4L2 and
H4L4 have a metal : ligand ratio of 2 : 1 (Fig. 4). All
complexes of these ligands have square pyramidal or
octahedral structure. The results of elemental analyses
and ICPꢀOES the complexes are in good agreement
with the proposed formula. The IR data support the
proposed structure for the ligands and their comꢀ
plexes. The thermal analyses data of these chelates
shows that some of the complexes have one or two
mole crystallization water molecules. The complexes
were generally thermally decomposed in 4–6 succesꢀ
sive decomposition steps. The final decomposition
products are found to be the corresponding metal or
metal oxides. But in the some complexes, decomposiꢀ
tion of the compound did not finish completely at
1000oC. Therefore, we did not find last decomposition
product. Furthermore liquid–liquid extraction of
some transition metal ions (MnII, CoII, NiII, CuII, ZnII,
PbII, CdII, HgII) with the ligands have been examined.
All ligands behave as good extractants and complexing
agents for mercury(II) and can be used for mercury
recovery.
The CuII complex with the formula [Cu(H2L2)]
⋅
H2O was thermally decomposed in four successive
decomposition steps. The first estimated mass loss of
3.10% (calculated mass loss = 2.73%) within the temꢀ
perature range 40–150
eration of one H2O molecule. The second step occurs
within the temperature range 150–245 with an estiꢀ
°C can be attributed to the libꢀ
°C
mated mass loss 42.45% (calculated mass loss =
42.36%), which is reasonably accounted for the loss of
biphenyl, two Cl and two CO groups, and last steps is
decomposition of the compound completely leaving
Cu as residue with total estimated mass loss 90.65%
(total calculated mass loss = 90.36%).
The CoII complex, with the general formula
[Co(H2L4)]
⋅
2H2O, shows decomposition pattern of
five stages. The first step with estimated mass loss of
5.50%, found within the temperature range 30–105
°C.
Corresponding to loss of two H2O molecules (calcuꢀ
lated mass loss = 5.26%). The second and third steps
with estimated mass loss of 45.50%, found within the
temperature range 105–490°C. Corresponding to loss
of diphenylmethane, two Cl and two CO (calculated
mass loss = 45.21%). The remaining two decomposiꢀ
tion steps with an estimated mass loss 38.50% which is
due to decomposition of the compound completely
leaving CoO residue occurring within the temperature
ACKNOWLEDGMENTS
The authors gratefully acknowledge the Research
Süleyman Demirel University (Project
no. 1079 M 05) (IspartaꢀTurkey) for financial support.
Fund of
range 490–920°C (calculated mass loss = 38.58%).
The total estimated mass loss is 89.50% (total calcuꢀ
lated mass loss = 89.05%).
The NiII complex, with the general formula
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