Synthesis and complex formation of Di[4-(11-chloro-3,6,9-trioxaundecyloxy)-phenylamino]glyoxime

Article abstract of DOI:10.1081/SIM-100106860

Di[4-(11-chloro-3,6,9-trioxaundecyloxy)phenylamino]glyoxime (LH₂) has been prepared from 1-amino-4-(11-chloro-3,6,9-trioxaundecyloxy)benzene, anti-dichloroglyoxime, and sodium carbonate in ethanol. Nickel(II), copper(II) and cobalt(II) complexes of the ligand were synthesized. The Cu(II), Ni(II) and Co(II) complexes of the vic-dioxime ligand LH₂ have a metal/ligand ratio of 1:2 and the ligand coordinates only through the N, N atoms, as do most vicinal dioximes. The structures of the ligand and its complexes were investigated by elementel analyses, magnetic susceptibility measurements, ¹H NMR, IR and U.V.-Visible spectroscopy.

Full text of DOI:10.1081/SIM-100106860

Synthesis and Reactivity in Inorganic and Metal-Organic
Chemistry
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SYNTHESIS AND COMPLEX FORMATION OF
DI[4-(11-CHLORO-3,6,9-TRIOXAUNDECYLOXY)
PHENYLAMINO]GLYOXIME
Mükerrem Kurtoğlu & Selahattin Serin
To cite this article: Mükerrem Kurtoğlu & Selahattin Serin (2001) SYNTHESIS AND COMPLEX
FORMATION OF DI[4-(11-CHLORO-3,6,9-TRIOXAUNDECYLOXY) PHENYLAMINO]GLYOXIME,
Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry, 31:7, 1229-1237, DOI:
10.1081/SIM-100106860
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SYNTH. REACT. INORG. MET.-ORG. CHEM., 31(7), 1229–1237 (2001)
SYNTHESIS AND COMPLEX FORMATION
OF DI[4-(11-CHLORO-3,6,9-
TRIOXAUNDECYLOXY)-
PHENYLAMINO]GLYOXIME
1
Mukerrem Kurtoglu and Selahattin Serin*
,1,2
ꢀ
1Department of Chemistry, University of
_
Kahramanmaras Sutcu Imam, 46100,
Kahramanmaras, Turkey
E-mail: mkurtoglu@ksu.edu.tr
2Department of Chemistry, University of Cukurova,
01130, Adana, Turkey
E-mail: serin@ksu.edu.tr
ABSTRACT
Di[4-(11-chloro-3,6,9-trioxaundecyloxy)phenylamino]gly-
oxime (LH2) has been prepared from 1-amino-4-(11-chloro-
3,6,9-trioxaundecyloxy)benzene, anti-dichloroglyoxime, and
sodium carbonate in ethanol. Nickel(II), copper(II) and
cobalt(II) complexes of the ligand were synthesized. The
Cu(II), Ni(II) and Co(II) complexes of the vic-dioxime ligand
LH2 have a metal=ligand ratio of 1:2 and the ligand coordi-
nates only through the N, N atoms, as do most vicinal diox-
imes. The structures of the ligand and its complexes were
investigated by elementel analyses, magnetic susceptibility
1
measurements, H NMR, IR and U.V.-Visible spectroscopy.
*Corresponding author.
1229
Copyright # 2001 by Marcel Dekker, Inc.
www.dekker.com

ꢀ
KURTOGLU AND SERIN
1230
INTRODUCTION
Even though the chemistry of transition metal complexes with vic-
dioxime ligands has been well studied and has been the subject of several
reviews, only a few examples of the ligands with two vic-dioxime groups
have been reported174. Vic-dioximes have received considerable attention as
model compounds which mimic biofunctions such as the reduction of
vitamin B121,5. Oxime metal chelates are biologically active6 and semi-
conducting7,8
.
Both anti-dichloroglyoxime and cyanogendi-N-oxide, have been used
to prepare vic-dioxime derivatives9715. The addition reaction of either of
these two reactants with diamino compounds gives heterocyclic or macro-
heterocyclic dioximes. The first five-membered heterocyclic vic-dioxime, 1,3-
diphenyl-2-thioxa-4,5-bis(hydroximino)-imidazoline, was synthesized by the
reaction of diphenyl-1-thiourea with cyanogendi-N-oxide12. The (E,E)- and
(E,Z)-stereoisomers of vic-dioximes coordinate through their N,N or N,O
sites and, in a few cases, interconversion of (E,E)- and (E,Z)-complexes16718
is possible. In this article we describe the synthesis of a novel (E,E)-dioxime
(Fig. 1) and its complexes with the transition metal ions Ni(II), Cu(II) and
Co(II).
EXPERIMENTAL
Materials
All chemicals and solvents were of analytical grade and were used
without further purification. Dichloroglyoxime was prepared using known
procedures19,20. 1-Amino-4-(11-chloro-3,6,9-trioxaundecyloxy)benzene was
Figure 1. Structure of the ligand, LH2.

GLYOXIME COMPLEXES
1231
Figure 2. Proposed structure of the metal complexes.
prepared according to the literature method21. Cyanogen-di-N-oxide was
prepared as described by Grundmann et al.9
Physical Measurements
The elemental analyses were carried out with a Carlo Erba 1106
instrument. The 1H NMR spectrum of the ligand was obtained in DMSO-d6
on a Bruker Ar X250 MHz spectrometer. The electronic absorption spectra
of DMSO solutions of the ligand and complexes in the range 2007800 nm
were measured on a Shimadzu UV-160A spectrometer. IR spectral mea-
surements were taken on a Shimadzu FT-IR 8300 spectrometer.
Synthesis of Di[4-(11-chloro-3,6,9-trioxaundecyloxy)-
phenylamino]glyoxime, LH2
To
a
solution of 1-amino-4-(11-chloro-3,6,9-trioxaundecyloxy)
benzene (0.45 g, 1.48 mmol) in 50 mL of ethanol was added a solution of
cyanogen-di-N-oxide which was obtained by treating a suspension of anti-
dichloroglyoxime (0.091 g, 0.576 mmol) in dichloromethane with 1 N
Na2CO3 at ꢀ10 ꢁC. The mixture was stirred at the same temperature for 8 h.
The volume of the reaction mixture was reduced to 30 mL and the crystal-
lization completed at low temperature (ꢀ30 ꢁC). The white crystals were
filtered off, washed with cold ethanol and dried. The ligand was soluble in hot
ethanol and DMSO. Yield, 0.522 g (51%). M.p., 73774 ꢁC. 1H NMR (ppm,
DMSO-d6): 3.5573.65 (t, J ¼ 5.8, 4H, -CH2Cl), 3.6773.75 (m, 20H, g-Z-CH2),
3.86 (t, J ¼ 4.8, 4H, b-CH2), 4.15 (t, J ¼ 4.8, 4H, a-CH2), 6.60 (d, J ¼ 2.3, 4H,
Ar-H), 6.75 (d, J ¼ 2.3, 4H, Ar-H), 9.20 (s, 2H, N-H), 10.85 (s, 2H, OH). Uv.-
Vis. (nm, DMSO, Mꢀ1.cmꢀ1): 370 (e ¼ 14; 000), 275 (e ¼ 12; 200), 270

ꢀ
KURTOGLU AND SERIN
1232
(e ¼ 11; 150). IR (KBr, cmꢀ1): 3440 m (N-H), 3180 s (OH), 3045 w (Ar-C-H),
2962 s (CH2CH2), 1640 m (C›N), 1225 s (Ar-O-C), 1118 s (C-O-C), 930 m
(N-O). Elemental analyses for C30N4H44O10Cl2 (MW 691 g=mol)): Calcd: C,
52.10; N, 8.10; H, 6.37%. Found: C, 52.26; N, 8.22; H, 6.12%.
Synthesis of Ni(LH)2
A solution of NiCl2.6H2O (0.043 g, 0.181 mmol) in ethanol (20 mL)
a
was added to
solution of di[4-(11-chloro-3,6,9-trioxaundecylox-
y)phenylamino]- glyoxime, LH2, (0.25 g, 0.363 mmol) in ethanol (25 mL).
The reaction mixture was stirred at 45 ꢁC for 31=2 h. A solution of 0.1 M
NH3 in alcohol (10 mL) was then added (pH ¼ 3.5) and the resulting red
precipitate was filtered off, washed with water and ethanol and dried. Yield,
0.411 g (79%). M. p. 1307132 ꢁC. Uv.-Vis. (nm, DMSO, Mꢀ1.cmꢀ1): 407
(e ¼ 22; 300), 272 (e ¼ 16; 500), 260 (e ¼ 14; 300). IR (KBr, cmꢀ1): 3451 m
(N-H), 3053 w (Ar-C-H), 2960 s (CH2CH2), 1637 w (C›N), 1211 s (Ar-O-C),
1127 s (C-O-C), 925 m (N-O). Elemental analyses for C60N8H86O20Cl4Ni
(MW. 1438.5): Calcd: C, 50.05; N, 7.78; H, 5.90; Ni, 4.08%. Found: C,
49.88; N, 7.93; H, 6.05, Ni, 4.37%.
Synthesis of Cu(LH)2
Di[4-(11-chloro-3,6,9-trioxaundecyloxy)phenylamino]glyoxime
(0.47 g, 0.68 mmol) was dissolved in ethanol. To this solution was added a
solution of CuCl2.2H2O (0.0578 g, 0.34 mmol) in ethanol (15 mL). While
stirring and heating, a 1% NaOH solution in ethanol was added until the
pH became 4 and the mixture was then heated on a water bath for 4 h. The
formed dark brown complex was filtered, washed with alcohol and ether,
then dried. This complex is soluble in DMSO and DMF. Yield, 0.72 g
(73%). M. p. 1237124 ꢁC. meff (B.M): 1.85. Uv.-Vis. (nm, DMSO,
M
ꢀ1.cmꢀ1): 370 (e ¼ 18; 000), 275 (e ¼ 15; 200), 270 (e ¼ 14; 350). IR
(KBr, cmꢀ1): 3451 w (N-H), 3053 w (Ar-C-H), 2960 s (CH2CH2), 1630 w
(C›N), 1211 s (Ar-O-C), 1127 s (C-O-C), 925 m (N-O). Elemental analysis
for C60N8H86O20Cl4Cu (MW, 1438.5): Calcd: C, 49.88; N, 7.76; H, 5.96; Cu,
4.43%. Found: C, 49.72; N, 7.84; H, 5.85, Cu, 4.61%.
Synthesis of Co(LH)2
Di[4-(11-chloro-3,6,9-trioxaundecyloxy)phenylamino]glyoxime (0.25 g,
0.363 mmol) was dissolved in ethanol (15 mL) and to this solution was

GLYOXIME COMPLEXES
1233
added a solution of CoCl2.6H2O (0.043 g, 0.181 mmol) in ethanol. The
solution was treated with 1% NaOH solution in alcohol until the pH
became 4. Then the mixture was heated on a water bath for 4 h and allowed
to stand overnight. A brown complex was precipitated with ether. Yield,
0.395 g (75%). M.p.: 1367138 ꢁC. meff (B. M): 2.03. Uv.-Vis. (nm, DMSO,
M
ꢀ1.cmꢀ1): 395 (e ¼ 18; 550), 267 (e ¼ 15; 150), 260 (e ¼ 13; 750). IR
(KBr, cmꢀ1): 3449 w (NꢀꢀH), 3041 w (Ar-C-H), 2964 s (CH2CH2), 1633 w
(C›N), 1223 s (Ar-O-C), 1120 s (C-O-C), 927 m (NꢀꢀO). Elemental analyses
for C60N8H86O20Cl4Co (MW, 1439): Calcd: C, 52.10; N, 8.19; H, 6.37; Co,
4.42%. Found: C, 52.21; N, 8.19; H, 6.45, Co, 4.23%.
RESULTS AND DISCUSSION
Synthesis of Compounds
The ligand used for this study, di[4-(11-chloro-3,6,9-trioxaun-
decyloxy)phenylamino]glyoxime, contains two long chain polyether groups
and a vic-dioxime group. Its synthesis was accomplished in 51% yield by the
reaction of cyanogen-di-N-oxide which was obtained from (E,E)-dichlor-
oglyoxime and 1 N aqueous Na2CO3 solution and 1-amino-4-(11-chloro-
3,6,9-trioxaundecyloxy)- benzene in ethanol. The structure of the ligand is
shown in Fig. 1. The structure of LH2 ligand was confirmed by a combi-
1
nation of elemental analyses, H NMR, IR and UV-Vis spectral data.
The vic-dioxime ligand LH2 has been reacted with Ni(II), Cu(II) and
Co(II) chlorides to give the complexes as described by the following equa-
tion.
MCl2:mH2O þ 2LH2 ! MðLHÞ2 þ 2HCl þ mH2O
M ¼ NiðIIÞ; CuðIIÞ and CoðIIÞ
The experimental results of the elemental analyses of the ligand and
complexes are in agreement with theoretical expectations. The analytical
data show that the ligand LH2 forms 1:2 complexes with Ni(II), Cu(II) and
Co(II) ions. All of the metal complexes are stable in air and soluble in
dimethyl formamide (DMF) and dimethyl sulphoxide (DMSO). Magnetic
susceptibility measurements revealed that the complex Ni(LH)2 is diamag-
netic which is an expected property for nickel(II) complexes and that the
complexes Cu(LH)2 and Co(LH)2 are paramagnetic13,22. Magnetic sus-
ceptibility measurements were determined at 293 K on a Gouy balance.
Experimental magnetic susceptibilities were corrected for diamagnetism.
The magnetic susceptibility value of the Ni(LH)2 complex was calculated by

ꢀ
KURTOGLU AND SERIN
1234
the spin-only formula. The meff values of the complexes, Cu(LH)2 and
Co(LH)2, are 1.85 and 2.03 B.M., respectively.
1H NMR Spectra
The 1H NMR data of the ligand indicate an anti-configuration for the
vic-dioxime by virtue of the presence of only one singlet for N-OH protons
at the lower field of the spectrum (10.85 ppm, 2H)12. In the case of amphi-
dioximes, one of the OH proton is directed towards the N atom of the
adjacent hydroximino group and is participating in intramolecular hydro-
gen bonding (O-H. . . N). This results in two singlets observed for the OH
protons16. The NꢀꢀH proton signals were observed at higher field (9.20 ppm,
2H). The signals of the protons of the aromatic group appeared at 6.75 and
6.60 ppm as two close doublets. The 1H NMR spectrum of the ligand
showed two triplets at 3.86 and 4.15 ppm for the Ar-OCH2CH2 protons23.
The rest of the ether methylene protons appeared as multiplets at 3.5573.63
and 3.6773.75 ppm. The results are consistent with those reported for
oxyethylene groups attached to a benzene ring in crown ethers or chains.
IR Spectra
In the IR spectrum of the LH2 ligand, the O-H stretching vibration is
observed at 3180 cmꢀ1 as a broad absorption band. Ar-CH, C›N and N-O
stretches are observed at 3045, 1640 and 960 cmꢀ1, respectively24,25. In
addition to these, a narrow band at about 3440 cmꢀ1 implies the presence of
a N-H group. These values are in harmony with previously reported dia-
minoglyoxime derivatives. The bands at 1225 and 1118 cmꢀ1 in the spectrum
of the LH2 vic-dioxime ligand are the bands corresponding to the streching
of Ar-O-C and C-O-C ether groups26728. In the IR spectra of the metal
complexes, Ni(LH)2, Cu(LH)2 and Co(LH)2, the weak bands at 1720, 1710,
1715 cmꢀ1, respectively, may be assigned to intramoleculer hydrogen bridge
(O-H. . . O) bending vibrations29. The disappearence of the stretching
vibrations of the OH band at 3180 cmꢀ1, which was present in the free
ligand, is further evidence for O-HÁ Á ÁO bond formation.
UV-Visible Spectra
The UV-Visible spectra of all compounds were measured in DMSO
solutions. In the UV-Visible spectrum of LH2, the band belonging to the
C›N group is observed at 370 nm. b-Bands belonging to aromatic rings

GLYOXIME COMPLEXES
1235
appear at 275 nm. In the spectra of the metal complexes, the bands in the
2757270 nm range can be attributed to the p ! pà transitions of the ben-
zenoid rings. In a like manner, the bands observed in the 4297362 nm range
are also assigned to charge-transfer bands.
ACKNOWLEDGMENT
The authors are thankful to the Institue of Science, University of
Cukurova, Adana, Turkey, for financial support (Project No: FBE.97.124).
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Received November 16, 2000
Accepted June 6, 2001
Referee I: D. P. Rillema
Referee II: R. F. Cunico