Synthesis and complex formation of unsymmetrically substituted arylthio-p-chlorophenyl vic-dioximes

Article abstract of DOI:10.1081/SIM-120005619

anti-Chlorophenylchloroglyoxime, 4-ClC₆H₄C(=NOH)CCl-(=NOH), has been synthesized by chlorination of anti-p-cholorophenylglyoxime. The reaction of 4-ClC₆H₄C-(=NOH)CCl(=NOH) with thiophenol, 4-methylthiophenol and

Full text of DOI:10.1081/SIM-120005619

Synthesis and Reactivity in Inorganic and Metal-Organic
Chemistry
ISSN: 0094-5714 (Print) 1532-2440 (Online) Journal homepage: http://www.tandfonline.com/loi/lsrt19
SYNTHESIS AND COMPLEX FORMATION OF
UNSYMMETRICALLY SUBSTITUTED ARYLTHIO-p-
CHLOROPHENYL vic-DIOXIMES
H. Cahit Sevindir
To cite this article: H. Cahit Sevindir (2002) SYNTHESIS AND COMPLEX FORMATION OF
UNSYMMETRICALLY SUBSTITUTED ARYLTHIO-p-CHLOROPHENYL vic-DIOXIMES, Synthesis
and Reactivity in Inorganic and Metal-Organic Chemistry, 32:6, 1023-1031, DOI: 10.1081/
SIM-120005619
To link to this article: http://dx.doi.org/10.1081/SIM-120005619
Published online: 15 Feb 2007.
Submit your article to this journal
Article views: 12
View related articles
Full Terms & Conditions of access and use can be found at
http://www.tandfonline.com/action/journalInformation?journalCode=lsrt19
Download by: [Universite Laval]
Date: 15 July 2016, At: 08:07

MARCEL DEKKER, INC. • 270 MADISON AVENUE • NEW YORK, NY 10016
©2002 Marcel Dekker, Inc. All rights reserved. This material may not be used or reproduced in any form without the express written permission of Marcel Dekker, Inc.
SYNTHESIS AND REACTIVITY IN INORGANIC AND METAL-ORGANIC CHEMISTRY
Vol. 32, No. 6, pp. 1023±1031, 2002
SYNTHESIS ANDCOMPLEX FORMATION
OF UNSYMMETRICALLY SUBSTITUTED
ARYLTHIO-p-CHLOROPHENYL
vic-DIOXIMES
H. Cahit Sevindir
Department of Environmental Engineering,
Faculty of Engineering, Suleyman Demirel University,
32260 Isparta, Turkey
E-mail: sevindir@mmf.sdu.edu.tr
ABSTRACT
anti-Chlorophenylchloroglyoxime, 4-ClC6H4CEˆNOH)CCl-
EˆNOH), has been synthesized by chlorination of anti-
p-cholorophenylglyoxime. The reaction of 4-ClC6H4C-
EˆNOH)CClEˆNOH) with thiophenol, 4-methylthiophenol
and 4-methoxythiophenol in ethanol between À5 and À10 ꢀC
gives the unsymmetrical vic-dioximes, designated as thiophe-
nolo-p-chlorophenylglyoxime, 4-ClC6H4CEˆNOH)CESC6H5)-
EˆNOH),
4-methylthiophenolo-p-chlorophenylglyoxime,
4-ClC6H4CEˆNOH)CESC6H4-CH3-p)EˆNOH), and 4-metho-
xythiophenolo-p-chlorophenylglyoxime, 4-ClC6H4CEˆNOH)-
CESC6H4-OCH3-p)EˆNOH). The CuEII) and NiEII) complexes
of these ligands were prepared and are proposed to be square-
planar, while the corresponding CoEII) complexes are proposed
to be octahedral with water molecules as axial ligands. The
1023
DOI: 10.1081=SIM-120005619
Copyright # 2002 by Marcel Dekker, Inc.
0094-5714 EPrint); 1532-2440 EOnline)
www.dekker.com

1024
SEVINDIR
1
structural assiguments are supported by H NMR, IR and
elemental analyses.
INTRODUCTION
The transition metal complexes of vic-dioximes have been of particular
interest as biological model compounds.[1] The substitution pattern of
the vic-dioxime moiety a€ects the structure and stability of the complexes,
e.g., CoEII) complexes of dialkyl- or diarylglyoxime and dithioglyoxime
derivatives can be obtained by the reduction of octahedral CoEIII)
compounds,[4,8] but the complexes are decomposed in the case of diamino-
glyoxime derivatives.[2]
In the present paper, we report the synthesis and complex formation of
three new substituted arylthioglyoximes as examples of unsymmetrically
substituted vic-dioximes. The asymmetry of the ligands is expected to
enhance the solubility of planar complexes derived from them. A general
formula for the ligands is shown in Fig. 1.
RESULTS ANDDISCUSSION
The number of vic-thiodioximes and thiooximes in the literature[3,5,6]
is rather small. The structures of the ligands have been veri®ed by elemental
1
analyses, H NMR and IR spectral data. The elemental analysis results are
given in Table I.
Figure 1. General formulas of ligands.

COMPLEXES OF VIC-DIOXIMES
1025

1026
SEVINDIR
1H NMR Spectra of Ligands and Complexes
1
In the H NMR spectra of the ligands two deuterium-exchangeable
singlets were observed, corresponding to two non-equivalent OH protons,
which also indicate the anti-con®guration of the OH groups relative to each
other.[7] When the chemical shift values of the two OH groups in the three
ligands are compared, the peaks at lower ®eld vary little E12.00711.90 ppm,
D ˆ 0.1 ppm), while a considerable di€erence is observed for those at higher
®eld E10.50710.30 ppm, D ˆ 0.2 ppm) ETable II). The former is assigned to
the OH proton adjacent to the phenyl groups, and the latter to the OH
proton of the arylthio-oxime group, since the e€ect of various substituents
is expected to be higher on the arylthio-oxime group. The methyl protons
are seen at2.15 ppm as singlets.
The solubility of the complexes prepared from the three new unsym-
1
metrical ligands is not sucient to obtain H NMR spectra in solution on
our 100 MHz instrument except for NiEL1)2. The proton NMR spectrum of
this diamagnetic complex indicates OÀÀHÁ Á ÁO bridge formation by the
strong shift of the OH protons to lower ®eld E15.20 ppm) compared to the
ligand.[2,7,10]
As a consequence of the asymmetry in the ligands, the complexes
are expected to form two isomers EFig. 2). TLC Esilicagel-G) was
employed with di€erent solvent mixtures and varying polarities, but
only one spot appears in each case. This result implies the formation of
only one isomer under these reaction conditions. The geometric
1
isomerism of NiEL1)2 can be inferred from the H NMR spectrum, since
Table II. 1H NMR Dataa Ein ppm) for the Ligands Ein DMSO-d6) and NiEII)
Complex Ein CF3COOH)
Compound
HL1
O-Hb
O-Ha
OÀÀHÁ Á ÁO
OCH3
HEarom).
CH3
11.98
Es, 1H)
7
10.33
Es, 1H)
7
7
7
7.6476.61
Em, 9H)
7.5477.88
Em, 18H)
7.8676.75
Em, 8H)
7
NiEL1)2
HL2
15.20
Es, 2H)
7
7
7
7
11.90
10.50
2.15
Es, 3H)
7
Es, 1H)
12.00
Es, 1H)
Es, 1H)
10.30
Es, 1H)
HL3
7
3.63
Es, 3H)
7.7776.81
Em, 8H)
as: singlet; m: multiple.
bDisappears on D2O exchange.

COMPLEXES OF VIC-DIOXIMES
1027
Figure 2. Square-planar and octahedral metal complexes of the unsymmetrical li-
gands HL1, HL2, and HL3. All complexes are suggested to exist in the trans-form.
the alternative chemical environments will show two OÀÀH Á Á Á O bridge
protons in the cis-form, butonly one in ht e trans-structure. The observed
spectrum has only one resonance at 15.20 ppm implying the trans-form of
the complex.

1028
SEVINDIR
IR Spectra of Ligands and Complexes
In the IR spectra of the ligands, C-S E6807660 cmÀ1), OH E32307
3260 cmÀ1), CˆN E165071610 cmÀ1), and NO E9807950 cmÀ1) stretches
appear at frequencies expected for substituted glyoximes[9712] ETable III).
The characteristic IR absorptions of the complexes are given in Table III.
The metal-ligand ratio in all of the complexes is 1:2, but the CoEII) com-
plexes have coordinated two additional water molecules for each Co ion.
Thus, it is reasonable to propose an octahedral structure for the CoEII) and
square-planar coordination for the NiEII) and CuEII) compounds EFig. 2).
The IR spectra of the complexes support these structures by the weak
bending vibration of the OÀÀHÁ Á ÁO bridges around 166071690 cmÀ1 and the
shiftof ht e C ˆN vibration to lower frequencies at 162071660 cmÀ1 due to
N,N-metal coordination.[7,10] In the case of the CoEII) complexes, the
coordinated H2O molecules were identi®ed by a broad OH absorption
around 304073060 cmÀ1 which retains its intensity even after heating at
100 ꢀC for 24 h under vacuum.
EXPERIMENTAL
All chemicals and solvents used were of ``Analytical Reagent''
EMerck) grade. anti-Chlorophenylchloroglyoxime, 4-ClC6H4CEˆNOH)-
Table III. Characteristic IR Bandsa EcmÀ1) of the Ligands and Their Complexes in
KBr
Compound
OH
CHarom. OÀÀHÁ Á ÁO
CˆN
N-O
C-S
C-CI
HL1
NiEL1)2
3240 s
7
7
7
3230 s
7
7
7
3260 s
7
7
3070 s
3030 s
3020 s
3040 s
3060 s
3040 s
3040 s
3050 s
3070 s
3020 s
3040 s
3060 s
7
1610 s
1640 s
1620 s
950 s 670 w 690 s
960 s 680 w 700 s
960 s 670 w 670 s
1680 m
1660 m
1675 m
7
1680 m
1690 m
1680 m
7
CuEL1)2
CoEL1)2EH2O)2
HL2
1640 m 970 s 680 w 700 s
1630 s
1650 s
1620 s
970 s 660 w 680 s
950 s 670 w 705 s
970 s 670 w 680 s
NiEL2)2
CuEL2)2
CoEL2)2EH2O)2
HL3
1620 m 960 s 675 w 700 s
1650 s
1660 s
1650 s
980 s 680 w 670 s
960 s 660 w 710 s
990 s 670 w 705 s
NiEL3)2
1680 m
1690 m
1685 m
CuEL3)2
CoEL3)2EH2O)2
7
1630 m 970 s 680 w 690 s
as: strong, m: medium, w: weak.

COMPLEXES OF VIC-DIOXIMES
1029
CClEˆNOH), was prepared by reported procedures.[14,15] 1H NMR spectra
were recorded on a Varian T 100-A spectrometer. IR spectra were recorded
on a Pye Unicam SP1025 spectrophotometer as KBr pellets. The elemental
analyses were determined at the TUBITAK Laboratory EScienti®c and
Technical Research Council of Turkey).
Synthesis of Substituted Arylthioglyoximes
To a stirred solution of anti-4-ClC6H4CEˆNOH)CClEˆNOH) E2.33 g,
0.01 mol) in absolute ethanol E20 mL) at À10 and À15 ꢀC was added
dropwise a solution of 0.01 mol of the thiol compound [thiophenol E0.11 g),
4-methylthiophenol E0.124 g), 4-methoxythiophenol E0.1 mL)] in a mixture
of 30 mL of absolute ethanol and 10 mL of diethyl ether in 30 min in a fume
hood. After addition of a 1% NaOH solution in ethanol to raise the pH to
4-5, the reaction mixture wasꢀfurther stirred for 2 h, diluted with 120 mL
water, and left overnight at 5 C. The resulting precipitate was ®ltered and
recrystallized from ethanol-water E1:2). The crystalline product was ®ltered,
washed with water and dried at room temperature.
Synthesis of the Ni+II), Cu+II), and Co+II) Complexes
Solutions of 0.5 mmol of the metal salts [NiCl2Á6H2O) E0.119 g),
CuCl2Á2H2O E0.086 g) and CoCl2Á6H2O E0.119 g)] in 20 mL absolute ethanol
were added to a solution of the ligand E1 mmol) [HL1 E0.306 g), HL2
E0.320 g), HL3 E0.25 mL)] dissolved in 30 mL of ethanol. The pH of the
mixtures dropped to 3.073.5 and the color turned to red-brown. After
addition of a 1% NaOH solution in ethanol to raꢀise the pH to 4.575, the
mixtures were stirred on a water bath at 50755 C for 20 min. The pre-
cipitated complexes were ®ltered while hot. They were then washed with
water, ethanol and diethyl ether. The complexes were then dried under
vacuum at100 ꢀC. The yields and melting points of the compounds are
noted in Table I. The complexes are soluble in CF3COOH and slightly
soluble in hotDMF or DMSO.
Yields: NiEL1)2, 0.555 g; NiEL2)2, 0.593 g; NiEL3)2, 0.656 g; CuEL1)2,
0.472 g; CuEL2)2, 0.456 g; CuEL3)2, 0.514 g; CoEL1)2EH2O)2, 0.529 g;
CoEL2)2EH2O)2, 0.645 g; CoEL3)2EH2O)2, 0.628 g.

1030
SEVINDIR
REFERENCES
1. Chakravorty, A. Structure Chemistry of Transition Metal Complexes
of Oximes. Coord. Chem. Rev. 1974, 13, 1714.
0
ꢀ
2. Gul, A.; Bekaroglu, O. Synthesis of N,N -BisE4-benzo[15-crown-5])-
diaminoglioxime and its Complexes with CopperEII), NickelEII), Co-
baltEII), PalladiumEII) and UranylEVI). J. Chem. Soc. Dalton Trans.
1983, 9712, 253772541.
ꢀ
3. Gok, Y.; Bekaroglu, O. Synthesis and Complex Formation of Stereo-
isomers of 1,3-Diphenyl-2-thioxo-4,5-bisEhydroxyimino)imidazoline.
Z. Anorg. Allg. Chem. 1983, 496, 1977204.
0
ꢀ
4. Ahsen, V.; Gokceli, F.; Bekaroglu, O. S,S -BisE4-benzo[15-crown-5])-
dithioglyoxime and its Complexes with CopperEII), NickelEII), Co-
baltEII), CobaltEIII), PalladiumEII), PlatinumEII) and PlatinumEIV).
J. Chem. Soc. Dalton Trans. 1987, 8, 182771831.
5. Alexandrou, N.E.; Nicolaides, D.N. 1,3-Addition Reactions of Cya-
nogen Di-N-oxide. J. Chem. Soc. 1969, 3, 231972321.
6. Barltrop, J.A.; Morgan, K.J. Organic Sulphur Compounds. Part II.
The Condensation of Benzothiazole-2-sulphenamide with Carbonyl
Compounds. PartIII. J. Chem. Soc. 1957, 307273076.
ꢀ
7. Sevindir, H.C.; Mirzaoglu, R. The Synthesis of New BisEamino-R-
glyoximes) and Polyamidoxime Their Polymeric Metal Complexes.
Macromolecular Reports l994, A31, 3997410.
8. Schrauzer, G.N.; Kohnle, J. Coenzym B12-Modelle. Chem. Ber. 1964,
97, 305673064.
9. Buracevich, J.V.; Lore, A.M.; Volpp, G.P. Phenylglyoxime Separation,
Characterization and Structure of Three Isomers. J. Org. Chem. 1973,
36, 177.
10. Pekacar, A.I.; Ozcan, E. Synthesis and Complex Formation of Sub-
stituted Amino-p-Chlorophenylglyoximes of Unsymmetrical vic-Di-
oximes. Macromolecular Reports 1995, A32, 116171169.
11. Nakamura, A.; Konishi, A.; Otsuka. S. Chiral Metal Complexes Part 5
CobaltEII) and Some Other Transition Metal Complexes of Chiral vic-
Dioximate Ligands Derived from D-Camphor and L-b-Pinene. J.
Chem. Soc. Dalton Trans. 1979, 1, 4887495.
12. Sevindir, H.C. Synthesis of Ethane-1,2 bisEthio-R-glyoximes) and Their
ComplexeswithSomeTransitionMetals.Synth.React.Inorg.Met.-Org.
Chem. 2000, 30 E1), 1837190.
13. Norman, J.J.; Heggie, R.M.; Larose, J.B. Larose. Oximes I, The
Synthesis of Some Substituted 2-Oximinoacetophenones, Can. J.
Chem. 1962, 40, 154771553.

COMPLEXES OF VIC-DIOXIMES
1031
14. Houben, J.; Kaufmann. Uber Chlor-glyoxime, Oxin Derivate des
Oxalychlorids und Oxalsaure-halbchlorids und uber Cyan-formyl-
chloridoxin. Chem. Ber. 1913, 46, 282172835.
15. Grundmann, C.; Mini, V.; Dean S.M.; Frommeld, H.D. Dicyan-Di-N-
Oxyd. Ann. Chem. 1965, 687, 1917215.
Received March 28, 2001
Accepted March 29, 2002
Referee I: K. Moedritzer
Referee II: A. T. Odom