The synthesis and characterization of substituted aminomethylglyoximes and aminophenylglyoximes and their complexes with some transition metals

Article abstract of DOI:10.1081/SIM-120020328

In this study, six new unsymmetrical vic-dioximes, N-(3,4-dimethylphenyl)aminomethylglyoxime (L¹H₂), N-(3-chloro-4-methylphenyl)aminomethyl-glyoxime (L²H₂), N-(2,6-dimethylphenyl)aminomethylglyoxime (L³

Full text of DOI:10.1081/SIM-120020328

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The Synthesis and Characterization of Substituted
Aminomethylglyoximes and Aminophenylglyoximes and
Their Complexes with Some Transition Metals
a
Ayşin Zülfikaroğlu a , Murat Taş a , Hümeyra Batı a & Bekir Batı
a Department of Chemistry , Faculty of Science and Art , Ondokuzmayıs University , 55139,
Samsun, Turkey
Published online: 15 Feb 2007.
To cite this article: Ayşin Zülfikaroğlu , Murat Taş , Hümeyra Batı & Bekir Batı (2003) The Synthesis and Characterization of
Substituted Aminomethylglyoximes and Aminophenylglyoximes and Their Complexes with Some Transition Metals, Synthesis
and Reactivity in Inorganic and Metal-Organic Chemistry, 33:4, 625-638, DOI: 10.1081/SIM-120020328
To link to this article: http://dx.doi.org/10.1081/SIM-120020328
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SYNTHESIS AND REACTIVITY IN INORGANIC AND METAL-ORGANIC CHEMISTRY
Vol. 33, No. 4, pp. 625–638, 2003
The Synthesis and Characterization of
Substituted Aminomethylglyoximes
and Aminophenylglyoximes and
Their Complexes with Some
Transition Metals
*
Ays¸in Zu¨lfikarog˘lu, Murat Tas¸, Hu¨meyra Batı,
and Bekir Batı
Department of Chemistry, Faculty of Science and Art,
Ondokuzmayıs University, Samsun, Turkey
ABSTRACT
In this study, six new unsymmetrical vic-dioximes, N-(3,4-dimethyl-
phenyl)aminomethylglyoxime (L1H2), N-(3-chloro-4-methylphenyl)ami-
nomethyl-glyoxime (L2H2), N-(2,6-dimethylphenyl)aminomethyl-
glyoxime (L3H2), N-(3,4-dimethylphenyl)aminophenylglyoxime (L4H2),
N-(3-chloro-4-methylphenyl)-aminophenylglyoxime (L5H2) and N-(2,6-
dimethylphenyl)aminophenylglyoxime (L6H2) have been synthesized
from chloromethylglyoxime or chlorophenylglyoxime and the corres-
ponding substituted aromatic amines. The Co(II), Ni(II) and Cu(II)
*
Correspondence: Hu¨meyra Batı, Department of Chemistry, Faculty of Science and
Art, Ondokuzmayıs University, 55139 Samsun, Turkey; E-mail: hbati@omu.edu.tr.
625
DOI: 10.1081/SIM-120020328
0094-5714 (Print); 1532-2440 (Online)
www.dekker.com
Copyright D 2003 by Marcel Dekker, Inc.

626
Zu¨lfikarog˘lu et al.
complexes of these ligands were prepared. The structures of these new
1
ligands and their complexes are proposed based upon IR, UV-Vis, H
NMR spectral data, magnetic measurements, and elemental analyses.
Key Words: Aminomethylglyoximes; Aminophenylglyoximes; Vic-
dioxime.
INTRODUCTION
Oxime/oximate metal complexes have been investigated actively since
the beginning of the last century of the last millennium.[1] In general, oxime
and dioxime derivatives are very important compounds in the chemical
industry and in medicine. Technetium(V)- and copper(II)-containing vic-
dioximes currently are used as cerebral and myocardial perfusion imaging
agents.[2] Some oximes and their alkyl, oxyalkyl and amino derivatives
have been proven to have physiological and biological activity.[3] Various
Figure 1. The structures of the ligands.

Aminomethylglyoximes Complexes
627
substituted phenylaminoglyoxime ligands and their complexes with
transition metals have been reported.[4–11]
In this work, substituted phenylaminomethylglyoximes, substituted
phenylaminophenylglyoximes and their metal complexes have been syn-
thesized, extending our previous work,[4–6] and the objective was to add
new complexes to the literature of coordination chemistry. The molecular
strucures, designations and names of the new ligands are given in Figure 1.
RESULTS AND DISCUSSION
In this study, six new ligands have been prepared by the reaction of
substituted aromatic amines with chloromethylglyoxime or chlorophenyl-
glyoxime. The general reaction for the formation of metal complexes is
shown below and their strucures are given in Figure 2.
2 LxH2 þ M2þ ! ðLxHÞ2M þ 2Hþ
M ¼ NiðIIÞ; CuðIIÞ and CoðIIÞꢀ2H2O; x ¼ 1--6
The structures of the ligands and their complexes have been verified by
1
IR, UV-Vis, H NMR spectral data, magnetic measurements and elemental
analyses (Tables 1–4).
1H NMR Spectra of Ligands and Complexes
In the 1H NMR spectra of the ligands (Table 1), two peaks are
observed for the O–H protons in the substituted aminomethylglyoximes and
amino-phenylglyoximes because of the difference in neighboring oxime
groups. When the chemical shift values of the two O–H groups are
compared in the six different ligands, the ones at lower field quite closely
resemble each other (10.50–10.30 ppm for L1H2–L3H2, 10.89–10.48 ppm
for L4H2–L6H2) while a considerably larger difference is observed for the
Figure 2. Suggested structures of the complexes, M=Ni(II), Cu(II) and Co(II)ꢀ-
2H2O (For R see Figure 1).

628
Zu¨lfikarog˘lu et al.
Table 1. 1H NMR spectraa of the ligands and Ni(II) complexes in DMSO–d6
(d ppm).
CH3–
C=N
Compound O–H–O
O–H
O–H
Harom.
N–H
CH3
L1H2
–
10.37 s 9.63 s 6.85–
6.66 m
10.50 s 9.92 s 7.25–
6.65 m
7.30–
6.60 m
10.30 s 9.27 s 6.64–
6.40 m
7.03 s
10.89 s 9.60 s 7.57–
6.72 m
7.15–
6.53 m
10.93 s 9.84 s 7.40–
7.06 m
7.26–
5.94 m
10.48 s 9.20 s 7.18–
6.90 m
6.85–
6.40 m
7.96 s 1.87 s 2.12 s
7.96 s 2.01 s 2.22 s
9.07 s 1.79 s 2.09 s
6.96 s 1.90 s 2.10 s
8.60 s 1.35 s 2.11 s
L2H2
–
(L2H)2Ni
L3H2
16.70 s
–
–
–
(L3H)2Ni
L4H2
15.28 s
–
–
–
7.98 s
8.95 s
7.60 s
8.40 s
–
–
–
–
–
–
–
2.10 s
1.94 s
2.23 s
2.18 s
2.10 s
2.09 s
(L4H)2Ni
L5H2
15.86 s
–
–
–
(L5H)2Ni
L6H2
16.58 s
–
–
–
(L6H)2Ni
15.16 s
–
–
–
as=singlet, m=multiplet.
one at higher field (9.92–9.27 ppm for L1H2–L3H2, 9.84–9.20 ppm for
L4H2–L6H2). The N–H protons near the oxime group were observed at
9.07–6.96 ppm, aromatic C–H protons at 7.57–5.94 ppm and aliphatic
C–H protons at 2.23–1.94 ppm. There is also a singlet at 2.01–1.35 ppm
for CH3 protons of the CH3–C=N– groups. These values are in good
agreement with the similar vic-dioximes.[3–12]
1
The H NMR spectrum of the diamagnetic Ni(II) complexes indicate
O–H–O bridge formation resulting in a strong shift of the OH protons to
lower field (16.7–15.1 ppm) compared to the free ligands.[9,11,12]
As a consequence of the asymmetry in the ligands, the complexes are
expected to form two isomers: cis and trans. In order to isolate these two
isomers, TLC technique (silica gel–G) was employed with different solvent
mixtures and varying polarities, but only one product has been seen in each
case. This result implies the formation of only one isomer under these

Aminomethylglyoximes Complexes
629
Table 2. Magnetic moments of the complexes and characteristic IR bands of the
ligands and their complexes as KBr pellets (cm–1).
Meff
(BM)a
Compounds
L1H2
N–H
O–H
C=N
O–H–O
–
N–O
969 s
–
3405 m 3330–
3310 m
1657 s
(L1H)2Ni
(L1H)2Cu
(L1H)2Coꢀ2H2O
Dia
3285 s
3438 m
–
–
–
1597 m
1640 m
1590 m
1745 w
1777 w
1730 w
995 s
968 s
998 m
1.47
1.65
3410–
3267 m
3200–
3100 m
L2H2
–
3428 s
1656 s
–
961 s
(L2H)2Ni
(L2H)2Cu
(L2H)2Coꢀ2H2O
Dia
3263 s
3429 w
–
–
1603 m
1641 m
1590 s
1782 w
1701 w
1700 w
967 s
970 s
957 m
1.45
1.88
–
3460–
3210 s
3380 m
–
L3H2
–
3457 s
3315 s
3440 m
–
1648 s
1590 m
1625 m
1593 s
–
963 m
989 m
971 m
940 m
(L3H)2Ni
(L3H)2Cu
(L3H)2Coꢀ2H2O
Dia
2.10
2.13
1807 w
1712 w
1737 w
–
3590–
3470 s
L4H2
–
3395 m 3200–
3180 s
1641 s
–
967 s
(L4H)2Ni
(L4H)2Cu
(L4H)2Coꢀ2H2O
Dia
3328 s
3436 m
–
–
–
1598 m
1635 m
1624 m
1774 w
1750 w
1724 w
961 s
998 s
1000 m
1.46
2.24
3430–
3380 m
L5H2
–
3490 s
3445 s
3438 m
–
3340 m
–
1645 s
1635 m
1605 m
1588 s
–
960 m
940 m
951 s
(L5H)2Ni
(L5H)2Cu
(L5H)2Coꢀ2H2O
Dia
1.46
2.51
1757 w
1690 w
1710 w
–
3510–
3400 s
943 m
L6H2
–
3361 m 3320–
3290 m
1634 s
–
988 s
(L6H)2Ni
(L6H)2Cu
(L6H)2Coꢀ2H2O
Dia
1.5
3314 s
3490 m
–
–
–
1633 m
1628 m
1630 s
1764 w
1697 w
1701 w
1095 m
1024 m
1026 m
2.06
3440–
3380 s
ameff: Magnetic moment, Dia: Diamagnetic, s: strong, m: medium, w: weak.

630
Zu¨lfikarog˘lu et al.

Aminomethylglyoximes Complexes
631

632
Zu¨lfikarog˘lu et al.
Table 4. Characteristic UV-Vis bands of the ligands and complexes in DMSO (nm).
ap ! p* and
an ! p* of
the ligands
and complexes
aCharge
transfer
Compounds
L1H2
ad ! d
222 (4270)
243 (8320)
303 (28540)
221 (11480)
270 (7320)
223 (16280)
302 (4200)
223 (18840)
248 (4920)
290 (7620)
231 (2140)
245 (4480)
291 (7250)
228 (19980)
264 (15220)
214 (18390)
275 (16010)
225 (26880)
272 (12780)
221 (1450)
244 (4090)
290 (2480)
219 (19600)
274 (6880)
314 (3920)
226 (19140)
268 (7980)
222 (18420)
257 (10560)
317 (4700)
238 (2550)
260 (1580)
290 (5270)
222 (19740)
262 (14800)
233 (19840)
280 (10560)
222 (18020)
264 (8160)
–
–
–
(L1H)2Ni
360 (3690)
370 (2300)
–
1A1g ! B1g
1A1g ! A2g
540 (650)
–
1
1
458 (1280)
(L1H)2Cu
2B1g ! A1g
2
586 (200)
–
(L1H)2Coꢀ2H2O
–
–
L2H2
–
–
(L2H)2Ni
(L2H)2Cu
(L2H)2Coꢀ2H2O
L3H2
363 (3020)
386 (3130)
358 (5600)
–
1A1g ! B1g
1A1g ! A2g
1
1
455 (980)
2
536 (200)
–
2B1g ! A1g
599 (740)
–
–
–
–
(L3H)2Ni
356 (1900)
1A1g ! B1g
1A1g ! A2g
1
1
444 (640)
538 (310)
(L3H)2Cu
374 (2400)
–
2B1g ! A1g
–
–
2
602 (360)
–
(L3H)2Coꢀ2H2O
L4H2
–
–
–
(L4H)2Ni
352 (4700)
387 (3280)
350 (4260)
1A1g ! B1g
1A1g ! A2g
1
1
485 (840)
559 (230)
–
(L4H)2Cu
2B1g ! A1g
2
600 (640)
–
(L4H)2Coꢀ2H2O
–

Aminomethylglyoximes Complexes
Table 4. Continued.
633
ap ! p* and
an ! p* of
the ligands
and complexes
aCharge
transfer
Compounds
L5H2
ad ! d
222 (2690)
245 (2920)
290 (4000)
214 (21500)
265 (17700)
231 (21200)
277 (18040)
222 (20200)
280 (10580)
222 (950)
–
–
–
(L5H)2Ni
(L5H)2Cu
(L5H)2Coꢀ2H2O
L6H2
374 (2900)
452 (2780)
358 (5760)
–
1A1g ! B1g
1A1g ! A2g
553 (220)
–
1
1
479 (800)
2
2B1g ! A1g
628 (802)
–
–
–
–
245 (2120)
290 (1720)
225 (12560)
264 (13210)
327 (7220)
213 (18920)
272 (7600)
222 (19240)
272 (8140)
1
1
(L6H)2Ni
–
1A1g ! B1g
1A1g ! A2g
464 (970)
551 (460)
2
(L6H)2Cu
383 (1840)
347 (4260)
2B1g ! A1g
–
–
602 (410)
–
(L6H)2Coꢀ2H2O
a(emax: L cm–1 mol–1).
1
reaction conditions. The H NMR spectrum of the Ni(II) complexes can be
evaluated to determine the isomer formed, since the various chemical
environments will show two O–H–O bridge protons in the cis-form, but
only one in the trans-structure. Since only one signal occurs at 16.70,
15.28, 15.86, 16.58 and 15.16 ppm, respectively, for the nickel complexes
of (LxH)ꢁ, (x=2–6), the trans-form of these complexes is confirmed
(Figure 2). This is in agreement with similar vic-dioxime complexes in the
literature.[8,11,12] Cu(II) and Co(II)complexes are paramagnetic; for this
1
reason they are not suitable for H NMR study.
IR Spectra of the Ligands and Complexes
In the IR spectra of the ligands, bands at 3428–3340, 3490–3100,
1657–1634 and 988–960 cm–1 belong to N–H, O–H, C=N and N–O
stretching vibrations, respectively. These values are in accord with those of

634
Zu¨lfikarog˘lu et al.
previously reported substituted vic-dioximes.[4–14] The IR spectral values
and the elemental analysis results of the ligands and their complexes are
given in Tables 2 and 3, respectively. The metal–ligand ratio in all of these
complexes is 1:2, but the Co(II) complexes additionally have coordinated
two water molecules to the Co ion. In the case of the Co(II) complexes, the
coordinated H2O molecules were identified by broad OH absorptions bands
around 3510–3210 cm–1 which keep their intensity even after heating at
110 °C for 24 h. Compounds containing the Co(DH)2 unit, where DH is the
mono-anion of dimethylglyoxime, such as vic-dioxime, make up the bulk of
a class of compounds known as cobaloximes, which contain two mono-
deprotonated dioxime ligands H-bonded to each other, with the results that
the 4-nitrogen donor atoms are nearly co-planar. The two remaining axial
coordination sites are occupied by two water molecules.[15] The two water
molecules in the Co(II) complexes are in trans position. Consequently, an
octahedral structure for the Co(II) and square-planar coordination for the
Ni(II) and Cu(II) compounds are proposed (Figure 2). The IR spectra of
the complexes confirm these structures by the weak bending vibration of
the O–H–O bridges around 1807–1690 cm–1 and the shift of the C=N
vibration to lower frequencies (1641–1588 cm–1) due to N,N-metal
coordination.[6,13,14]
Magnetic Measurements
The mononuclear Ni(II) complexes of these ligands are diamagnetic;
there are no unpaired electrons in the Ni(II) ions, suggesting square-planar
geometry.[12,14,16] The magnetic moment values (Table 2) of the Cu(II)
complexes are in the range 2.10–1.45 B.M, which is a consequence of one
unpaired electron in the Cu(II) (d9) system.[16,17] The Co(II) compounds are
low-spin, meff=2.51–1.65 B.M.
UV Spectra of the Ligands and Complexes
The electronic spectra of the ligands and soluble complexes in DMSO
are given in Table 4.
In the electronic spectra of the ligands and complexes, the bands at
327–290 and 280–213 nm were assigned to n !p* and p! p* tran-
sitions,[18,19] respectively. The electronic spectra of the Ni(II) complexes
1
1
exhibit two bands at 559–536 and 485–444 nm assignable to A1g ! A2g
1
(b2g* !b1g*) and 1A1g ! B1g (a1g* !b1g*) transitions, respectively, support-
ing a square-planar geometry.[19–21] In the electronic spectra of these com-
plexes there are intense charge transfer bands at 374–352 nm.
The Cu(II) complexes show a broad band at 628–586 nm, which can be
2
2
assigned to a B1g ! A1g transition. This, together with the measured meff

Aminomethylglyoximes Complexes
635
values suggests square-planar geometry.[17,21,22] There is no weak d–d
transition observed in the Co(II) complexes. There are intense charge transfer
bands at 452–370 nm for Cu(II) and at 358–347 nm for Co(II), respectively.
EXPERIMENTAL
Chloromethylglyoxime and chlorophenylglyoxime were prepared ac-
cording to the methods reported in the literature.[23,24] All reagents were of
commercially available reagent grade and were used without further puri-
fication unless otherwise stated. IR spectra were recorded on a Matson-1000
1
FT-IR spectrophotometer in KBr pellets. H NMR spectra were recorded on
a Bruker 200 MHz FT-NMR spectrometer utilising deuterated dimethyl
sulfoxide as solvent. The magnetic susceptibilities were measured using a
Sherwood Scientific MX1 model Gouy magnetic susceptibility balance at
room temperature. UV-Vis spectra were recorded with a Unicam UV-Visible
spectrometer in absolute ethanol for the ligands and DMSO for the com-
plexes. pH measurements were done with a Gresiger Electronic GPHR 1400
pH meter. C, H and N analyses were performed by the TUBITAK Labratory
(Centre of Science and Technology Research of Turkey) in Izmit.
Synthesis of the Ligands
To a stirred solution of chloromethylglyoxime (2.73 g, 0.02 mol) or
cholorophenylglyoxime (3.97 g, 0.02 mol) in absolute ethanol (20 mL) at
ꢁ10 °C was added drop-wise a solution of 0.02 mol of the substituted
aromatic amine (2.42 g 3,4-dimethylaniline, 2.83 g 3-chloro-4-methylani-
line or 2.44 g 2,6-dimethylaniline) in absolute ethanol (25–30 mL) in 30
min. The reaction mixture was further stirred for 18–20 h at ꢁ10 °C.
L1H2
After adjusting the pH of the mixture to 5–5.5 with 1% KOH the
solution was stirred for additional 1–2 h at room temperature. The solution
was evaporated and then the product was recrystallized from CCl4, yield
1.78 g (40%).
L2H2, L3H2, L4H2, L5H2 and L6H2
After adjusting the pH of the mixture to 5–5.5 with 1% KOH the
solution was stirred further for 1–2 h at ꢁ5 °C. The solution was then
diluted with 100–120 mL of water and left overnight at 0 °C. The pre-
cipitated ligands were filtered and then recrystalized from ethanol–water

636
Zu¨lfikarog˘lu et al.
(1:2). Finally, the resulting precipitate was filtered, washed with water and
dried in vacuo at room temperature. Yields: 2.18 g (44%) (L2H2), 1.9 g
(43%) (L3H2), 4.14 g (74%) (L4H2), 5.77 g (95%) (L5H2) and 4.3 g (76%)
(L6H2). Some physical properties and spectral data of these compounds are
given in Tables 1–4.
Synthesis of Ni(II), Cu(II), and Co(II) Complexes
A solution of 2 mmol of the metal salt (0.48 g NiCl2ꢀ6H2O, 0.34 g
CuCl2ꢀ2H2O or 0.48 g CoCl2ꢀ6H2O) in 10 mL absolute ethanol was added
to a solution of 4 mmol of the ligand (0.89 g L1H2, 0.96 g L2H2, 0.89 g
L3H2, 1.13 g L4H2, 1.21 g L5H2, 1.13 g L6H2) dissolved in 20 mL absolute
ethanol. The mixture was stirred for 3–4 h at room temperature. The
original pale yellow color of the solutions changed immediately to red for
Ni(II), dark-brown for Co(II) and dark-brown or dark-green for Cu(II) and
their pH values decreased from 6–7 to 2–2.5, which were then adjusted to
about 5–5.5 with 1% KOH solution. The turbid mixture was stirred in a
water bath at 40–50 °C for one hour in order to completely precipitate the
complex. The precipitated complex was filtered, washed with ethanol and
diethyl ether for the Ni(II) complexes and diethyl ether for the Cu(II) and
Co(II) complexes and dried in vacuo, at room temperature. The colors,
melting points and elemental analysis results of the compounds are given in
Table 3.
ACKNOWLEDGMENT
The authors give deep thanks to Ondokuz Mayıs University for re-
search funding.
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637
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Received: August 23, 2001
Accepted: December 30, 2002
Referee I: J. G. Wardeska
Referee II: P. J. Toscano