Journal of Molecular Structure xxx (2018) 1e7

Contents lists available at ScienceDirect

Journal of Molecular Structure

journal homepage: http://www.elsevier.com/locate/molstruc

The synthesis and investigation of different cobaloximines by

spectroscopic methods
Ahmet Kilic a, *, Mustafa Durgun b, Nuri Yorulmaz c, Rahime Yavuz a
a
Harran University, Art and Science Faculty, Chemistry Department, 63190, Sanliurfa, Turkey
b
Harran University, Faculty of Education, Department of Science Education, Şanlıurfa, Turkey
c
Harran University, Faculty of Arts and Sciences, Department of Physics, Şanlıurfa, Turkey

a r t i c l e i n f o a b s t r a c t

Article history: In the present work, firstly a novel monoxime (1) and unsymmetric dioxime ligand (LH2) (2) derived
Received 9 January 2018 from 4-(4-hydroxyphenyl)-2-butanone as ketone was prepared under optimum conditions. Then, the
Received in revised form cobaloxime complexes [(LH)2ClCoB] (B ¼ neutral base: 4-DAP ¼ 4-(dimethylamino)pyridine, 4-HP ¼ 4-
26 March 2018
hydroxypyridine, 4-CP ¼ 4-chloropyridine, 4-MP ¼ 4-methylpyridine, 4-EP ¼ 4-ethylpyridine, 4-
Accepted 27 March 2018
Available online xxx
TBP ¼ 4-tert-butylpyridine and P ¼ pyridine) (3e9) with respect to varied axial groups were synthe-
sized in a two-necked round-bottom reaction flask by direct contact of dioxime ligand (2), and different
neutral base without special requirement of any additional chemical process. The prepared dioxime
Keywords:
Dioxime ligand
ligand (2) and its cobaloxime complexes (3e9) were characterized by means of NMR, FT-IR, UVeVis and
Cobaloximes LC-MS spectroscopy, melting point and magnetic susceptibility measurements as well as elemental
Characterization analysis. It is noteworthy that the coordination chemistry of this cobaloxime complexes is versatile,
Spectroscopy which is closely related to the nature of the unsymmetric dioxime ligand (2) derived from 4-(4-
Axial bases hydroxyphenyl)-2-butanone, as indicated by the results of the corresponding spectroscopic studies.
Also, the spectroscopic results demonstrated that the proposed cobaloxime complexes are a six-
coordinated species and octahedral geometry.
© 2018 Elsevier B.V. All rights reserved.

1. Introduction
Because they were previously proposed as good models of
Vitamin B12 and related compounds in various metabolisms, over
the past four decades, cobaloxime compounds have gained the
attention in coordination chemistry, organometallic chemistry,
bioinorganic chemistry and broad-scope potential applications.
Because their ease of synthesis and characterization and the reac-
tivity of CoeC bond of cobaloximes have provided an experimental
test of this approach, the cobaloxime complexes have allowed the
investigation of several properties such as the reactivity of CoeC
bond and the influence of the axial base on the binding energy of
the organo-ligand with the long-term goal to get insight into the
yet unestablished mechanism for the hemolysis of the CoeC bond
by the AdoCbl-based enzymes [1e3]. The weakening of the CoeC
bond of cobaloxime complexes has been evaluated as an effect of
* Corresponding author. Harran University, Chemistry Department, TR-63290,
Sanlıurfa, Turkey.
E-mail addresses: kilica63@harran.edu.tr, kilica63@hotmail.com (A. Kilic).
the steric as well as electronic properties of the various axial and
equatorial ligands [4] In addition; various symmetric or unsym-
metric dioxime ligand containing cobaloxime compounds are
bench stable and could be easily prepared in high yields [5].
Six-coordinated cobaloxime complexes formed from the
different symmetric or unsymmetric dioxime ligands and various
axial and equatorial ligands interactions have emerged in the past
few years as one of the most efficient series of molecular catalysts
for hydrogen evolution, and a significant number of studies have
been performed to understand the mechanisms of their electro-
and photocatalytic activities, due to the low overpotential required
[6e10]. However, we recently reported a new generation of coba-
loxime/organocobaloxime complexes incorporating different spe-
cies tetradentate dioxime ligand, which was shown to be
remarkable molecular catalysts for the fixation of CO2 to cyclic
carbonates [11e14]. Dreos et al. have reported that different orga-
nocobaloximes are good building blocks for the construction of
supramolecular structure by the reaction with functionalized aro-
matic boric acid [15,16]. Kumar and Gupta have reported the syn-
thesis and crystallographic studies of paddlewheel-based methyl
cobaloxime assembly formed from methyl cobaloxime, isonicotinic

https://doi.org/10.1016/j.molstruc.2018.03.121
0022-2860/© 2018 Elsevier B.V. All rights reserved.

Please cite this article in press as: A. Kilic, et al., The synthesis and investigation of different cobaloximines by spectroscopic methods, Journal of
Molecular Structure (2018), https://doi.org/10.1016/j.molstruc.2018.03.121
2 A. Kilic et al. / Journal of Molecular Structure xxx (2018) 1e7
acid and Zn(NO3)2 [17]. The N4 ring in the cobaloxime model
complexes is made up of two mono deprotonated different sym-
metric or unsymmetric dioxime ligands linked at two points by the
intermolecular hydrogen bond y(OeH/O). The result is essentially
planar macrocyclic dioxime ligands. Generally, the most common
cobaloxime or organocobaloxime compounds have been obtained
by using the dimethylglyoxime ligand [18]. In contrast to these
studies, in our previous published papers and in this study, the
obtained novel dioxime ligands were synthesized from various
ketones under optimum conditions.
In this paper, we describe a new the monoxime (1) from 4-(4-
hydroxyphenyl)-2-butanone as ketone and then dioxime ligand
(2) have been synthesized under suitable conditions. Then, the
structurally different cobaloxime (3e9) complexes were obtained
by use of CoCl2$6H2O in presence of different axial neutral bases in
EtOH solvent. We used various characterization techniques such as;
1
H and 13C NMR, FT-IR, UVeVis and LC-MS spectroscopy, melting
point measurements, magnetic susceptibility measurements and
elemental analysis for understanding of the spectroscopic proper-
ties of these compounds.
2. Experimental section
2.1. General considerations
All starting materials and other chemical compounds were
purchased from a commercial company and used without further
purification. Nuclear magnetic resonance (NMR) spectra were ac-
quired at 298 K on a Bruker 300 MHz Ultrashield TM 300 spec-
trometer (1H: 300 MHz; 13C: 75.0 MHz) in DMSO-d6 as solvent and
values are reported relative to the internal standard Me4Si. Chem-
ical shifts were reported in delta (d) units in ppm downfield from
TMS and J values are given in Hertz. Fourier transform infrared (FT-
IR) spectra were performed using a Perkin-Elmer Two UATR-FT
spectrophotometer in the range of 4000e400 cm1 at room tem-
perature with equipped ATR accessory. UVeVis absorption spectra
were measured on a Perkin-Elmer model Lambda 25 spectrometer
in the scan range of 200e1100 nm using quartz cuvettes at room
temperature and studied in C2H5OH and DMF. Elemental analyses
were conducted with a LECO CHNS 932 model analyzer and the
results were compared with the theoretical values. To understand
whether the target molecules occur, LC-MS spectra were obtained
on an Agilent LC-MS Spectrometer (LC-MS/MS). To determine the
melting point of the novel ligand and its cobaloxime complexes, an
Electrothermal 9100 melting point apparatus was used and values
were obtained without any correction. Magnetic Susceptibilities
were performed on a Sherwood Scientific Magnetic Susceptibility
Balance (Model MK1) at room temperature using Hg [Co(SCN)4] as
a calibrant; diamagnetic corrections were calculated from Pascal's
constants [19].
2.2. Synthesis of the monoxime (1) and dioxime ligand (LH2) (2)
In this study, the monoxime (1) and dioxime ligand (LH2) (2)
were prepared from 4-(4-hydroxyphenyl)-2-butanone under opti-
mum conditions, following the similar procedure with some
modifications [20]. The corresponding syntheses are briefly given
in Scheme 1.
Monoxime (1): Color: brown, yield (%): 84, m. p: 65  C,
Elemental Analysis (C10H11NO3, F. W: 193.2 g/mol): Calculated: C,
62.17; H, 5.74; N, 7.25. Found: C, 62.14; H, 5.71; N, 7.22. LC-MS (Scan
ESþ): m/z (%) 193.2 [M]þ. FT-IR (ymax/cm1): 3368 y(OeH), 3020
y(Ar-CH), 2949e2861 y(Aliph-CH), 1696 y(C]O), 1617 y(C]N),
1594e1511 y(C]C), 1228 y(NeO). 1H NMR (DMSO-d6, TMS,
300 MHz, d ppm): 9.62 (s, 1H, C]NeOH), 8.46 (s, 1H, HC]N), 6.96
Please cite this article in press as: A. Kilic, et al., The synthesis and investigation of different cobaloximines by spectroscopic methods, Journal of
Molecular Structure (2018), https://doi.org/10.1016/j.molstruc.2018.03.121
(d, 2H, J ¼ 8.4 Hz, AreCH), 6.64 (d, 2H, J ¼ 8.1 Hz, AreCH), 5.56 (s,
1H, AreOH), 2.64 (t, 2H, J ¼ 5.7 Hz, CH2eCH2) and 2.06 (s, 2H,
CH2eCH2). 13C NMR (DMSO-d6, TMS, 75 MHz, d ppm): 208.34 (C]
O), 155.40 (C]NOH), 175.15, 130.98, 128.97 and 115.04 (AreCH),
44.53 (CH2eCH2) and 29.70 (CH2eCH2). UVeVis (lmax/(nm),
* ¼ shoulder peak): 224, 278 and 324* (in C2H5OH); 238, 282 and
328* (in DMF).
Dioxime ligand (LH2) (2): Color: dark brown, yield (%): 80, m. p:
62  C, Elemental Analysis (C10H12N2O3, F. W: 208.2 g/mol): Calcu-
lated: C, 57.68; H, 5.81; N, 13.45. Found: C, 57.65; H, 5.78; N, 13.41%.
LC-MS (Scan ESþ): m/z (%) 208.2 [M]þ. FT-IR (ymax/cm1): 3378 and
3271 y(OeH), 3021 y(Ar-CH), 2961e2852 y(Aliph-CH), 1635 y(C]
N), 1550e1509 y(C]C), 1233 y(NeO). 1H NMR (DMSO-d6, TMS,
300 MHz, d ppm): 10.32 (s, 2H, C]NeOH), 8.56 (s, 1H, HC]N), 6.95
(d, 2H, J ¼ 8.4 Hz, AreCH), 6.67 (d, 2H, J ¼ 8.7 Hz, AreCH), 5.02 (s,
1H, AreOH), 2.65 (t, 2H, J ¼ 5.6 Hz, CH2eCH2) and 2.32 (t, 2H,
J ¼ 5.6 Hz, CH2eCH2). 13C NMR (DMSO-d6, TMS, 75 MHz, d ppm):
155.62 and 154.61 (C]NOH), 173.49, 131.08, 128.95 and 115.05
(AreCH), 31.24 (CH2eCH2) and 22.70 (CH2eCH2). UVeVis (lmax/
(nm), * ¼ shoulder peak): 226, 281 and 318* (in C2H5OH); 252, 281
and 325* (in DMF).
2.3. Synthesis of the cobaloxime complexes [(LH)2ClCoB] (3e9)
To a suitable round-bottomed flask containing 50 mL ethanol
(99.5%), dioxime ligand (LH2) (2) (1.0 g, 4.8 mmol) was added as one
portion and the solution was stirred in open air for 40 min for all
cobaloxime complexes (3e9). While the solution stirring,
CoCl2$6H2O (0.60 g, 2.4 mmol) was added as a solid and the solu-
tions turned green immediately. Then the resulting solutions were
refluxed for 5 h. Upon cooling to room temperature, 4- (dimethy-
lamino)pyridine (4-DAP) (0.33 g, 2.4 mmol) for [(LH)2ClCo(4-DAP)]
(3) complex, 4-hydroxypyridine (4-HP) (0.25 g, 2.4 mmol) for
[(LH)2ClCo(4-HP)] (4) complex, 4-chloropyridine (4-CP) (0.36 g,
2.4 mmol) for [(LH)2ClCo(4-CP)] (5) complex, 4-methylpyridine (4-
MP) (0.23 g, 2.4 mmol) for [(LH)2ClCo(4-MP)] (6) complex, 4-
ethylpyridine (4-EP) (0.27 g, 2.4 mmol) for [(LH)2ClCo(4-EP)] (7)
complex, 4-tert-butylpyridine (4-TBP) (0.35 g, 2.4 mmol) for
[(LH)2ClCo(4-TBP)] (8) complex, and pyridine (4-P) (0.19 g,
2.4 mmol) for [(LH)2ClCo(4-P)] (9) complex were added to mixtures
as a neutral base in the presence of air. The initial green solution
turned brown or dark brown upon a neutral base and 5.0 mL of
water addition. The air was passed through the mixtures for about
5 h. Then, the solvent of the filtrate was removed using rotary
evaporation and the desired complexes were isolated by filtration
as solids by crystallization from CHCl3/EtOH (1:3). After that, the
obtained products were washed with diethyl ether and hexane to
afford pure compounds.
[(LH)2ClCo(4-DAP)] (3): Color: brown, yield: % 68, m. p: >300  C,
Elemental Analysis (C27H32N6O6ClCo, F. W: 631.0 g/mol): Calcu-
lated: C, 51.40; H, 5.11; N, 13.32. Found: C, 51.37; H, 5.14; N, 13.29%.
meff ¼ Dia, LC-MS (Scan ESþ): m/z (%) 631.1 [M]þ. FT-IR (ymax/cm1):
3547 y(OeH), 3014 y(Ar-CH), 2960e2861 y(Aliph-CH), 1722
y(OeH/O), 1613 y(C]N), 1564e1443 y(C]C), 1231 y(NeO) and
532 y(CoeN). 1H NMR (DMSO-d6, TMS, 300 MHz, d ppm): 18.68 (s,
2H, OeH/O), 9.36 (s, 2H, HC]N), 7.70 (s, 4H, AreCH), 6.90 (s, 4H,
AreCH), 6.69 (s, 4H, AreCH), 4.52 (s, 2H, AreOH), 1.75 (s, 4H,
CH2eCH2), 1.29 (s, 4H, CH2eCH2) and 0.87 (s, 6H, N-(CH3)2). UVeVis
(lmax/(nm), * ¼ shoulder peak): 228, 260, 280 and 551* (in
C2H5OH); 234, 248, 269 and 597* (in DMF).
[(LH)2ClCo(4-HP)] (4): Color: brown, yield: % 66, m. p: >300  C,
Elemental Analysis (C25H27N5O7ClCo, F. W: 603.9 g/mol): Calcu-
lated: C, 49.72; H, 4.51; N, 11.60. Found: C, 49.70; H, 4.48; N, 11.57%.
meff ¼ Dia, LC-MS (Scan ESþ): m/z (%) 603.8 [M]þ. FT-IR (ymax/cm1):
3553 y(OeH), 3086 y(Ar-CH), 2969e2874 y(Aliph-CH), 1724
 A. Kilic et al. / Journal of Molecular Structure xxx (2018) 1e7 3

Scheme 1. The synthesis of the monoxime (1) and dioxime ligand (2) and its cobaloxime complexes (3e9); Reagents and conditions: (i) n-C4H9ONO, C2H5ONa, 5  C; (ii)
CH3COONa, NH2OH$HCl, EtOH, reflux; (iii) CoCl2$6H2O EtOH, reflux, B (pyridine derivatives), O2.

y(OeH/O), 1625 y(C]N), 1566e1445 y(C]C), 1234 y(NeO) and
504 y(CoeN). 1H NMR (DMSO-d6, TMS, 300 MHz, d ppm): 18.42 (s,
2H, OeH/O), 8.35 (s, 2H, HC]N), 7.76 (s, 4H, AreCH), 7.01 (s, 4H,
AreCH), 6.68 (s, 4H, AreCH), 4.26 (s, 2H, AreOH), 1.73 (s, 4H,
CH2eCH2), 1.28 (s, 4H, CH2eCH2) and 0.89 (s, 1H, AreOH). UVeVis
(lmax/(nm), * ¼ shoulder peak): 225, 254 and 268 (in C2H5OH);
235, 249, 272 and 640* (in DMF).
[(LH)2ClCo(4-CP)] (5): Color: pale brown, yield: % 62, m. p:
>300  C, Elemental Analysis (C25H26N5O6Cl2Co, F. W: 622.3 g/mol):
Calculated: C, 48.25; H, 4.21; N, 11.25. Found: C, 48.22; H, 4.18; N,
11.23%. meff ¼ Dia, LC-MS (Scan ESþ): m/z (%) 622.4 [M]þ. FT-IR (ymax/
cm1): 3547 y(OeH), 3023 y(Ar-CH), 2965e2857 y(Aliph-CH), 1724
y(OeH/O), 1611 y(C]N), 1536e1448 y(C]C), 1233 y(NeO) and
516 y(CoeN). 1H NMR (DMSO-d6, TMS, 300 MHz, d ppm): 18.79 (s,
2H, OeH/O), 8.86 (s, 2H, HC]N), 7.70 (s, 4H, AreCH), 6.85 (s, 4H,
AreCH), 6.66 (s, 4H, AreCH), 4.14 (s, 2H, AreOH), 1.36 (s, 4H,
CH2eCH2) and 0.88 (s, 4H, CH2eCH2). UVeVis (lmax/(nm),
* ¼ shoulder peak): 226, 256* and 284 (in C2H5OH); 232, 251, 267
and 642* (in DMF).
[(LH)2ClCo(4-MP)] (6): Color: brown, yield: % 69, m. p: >300  C,
Elemental Analysis (C26H29N5O6ClCo, F. W: 601.9 g/mol): Calcu-
lated: C, 51.88; H, 4.86; N, 11.66. Found: C, 51.84; H, 4.82; N, 11.64%.
meff ¼ Dia, LC-MS (Scan ESþ): m/z (%) 602.9 [MþH]þ. FT-IR (ymax/
cm1): 3553 y(OeH), 3012 y(Ar-CH), 2962e2856 y(Aliph-CH), 1721
y(OeH/O), 1612 y(C]N), 1553e1449 y(C]C), 1235 y(NeO) and
507 y(CoeN). 1H NMR (DMSO-d6, TMS, 300 MHz, d ppm): 18.24 (s,
2H, OeH/O), 9.26 (s, 2H, HC]N), 7.71 (s, 4H, AreCH), 6.98 (s, 4H,
AreCH), 6.68 (s, 4H, AreCH), 4.16 (s, 2H, AreOH), 1.72 (s, 4H,
CH2eCH2), 1.30 (s, 4H, CH2eCH2) and 0.87 (s, 3H, CeCH3). UVeVis
(lmax/(nm), * ¼ shoulder peak): 224, 255 and 286 (in C2H5OH);
236, 258, 286 and 680* (in DMF).
[(LH)2ClCo(4-EP)] (7): Color: brown, yield: % 68, m. p: >300  C,
Elemental Analysis (C27H31N5O6ClCo, F. W: 616.0 g/mol): Calcu-
lated: C, 52.65; H, 5.07; N, 11.37. Found: C, 52.62; H, 5.02; N, 11.34%.
meff ¼ Dia, LC-MS (Scan ESþ): m/z (%) 617.1 [MþH]þ. FT-IR (ymax/
cm1): 3548 y(OeH), 3020 y(Ar-CH), 2960e2854 y(Aliph-CH), 1729
y(OeH/O), 1616 y(C]N), 1554e1442 y(C]C), 1231 y(NeO) and
518 y(CoeN). 1H NMR (DMSO-d6, TMS, 300 MHz, d ppm): 19.36 (s,
2H, OeH/O), 9.23 (s, 2H, HC]N), 7.72 (s, 4H, AreCH), 7.01 (s, 4H,
AreCH), 6.67 (s, 4H, AreCH), 4.15 (s, 2H, AreOH), 2.07 (s, 2H,
CH2eCH3), 1.74 (s, 4H, CH2eCH2), 1.29 (s, 4H, CH2eCH2) and 0.88 (s,
3H, CH2eCH3). UVeVis (lmax/(nm), * ¼ shoulder peak): 228, 256
and 293 (in C2H5OH); 242, 256, 274 and 682* (in DMF).
[(LH)2ClCo(4-TBP)] (8): Color: dark brown, yield: % 72, m. p:
>300  C, Elemental Analysis (C29H35N5O6ClCo, F. W: 644.0 g/mol):
Calculated: C, 54.09; H, 5.48; N, 10.87. Found: C, 54.06; H, 5.44; N,
10.84%. meff ¼ Dia, LC-MS (Scan ESþ): m/z (%) 644.1 [M]þ. FT-IR
(ymax/cm1): 3547 y(OeH), 3047 y(Ar-CH), 2962e2864 y(Aliph-
CH), 1722 y(OeH/O), 1613 y(C]N), 1553e1426 y(C]C), 1230
y(NeO) and 526 y(CoeN). 1H NMR (DMSO-d6, TMS, 300 MHz,
d ppm): 17.38 (s, 2H, OeH/O), 9.26 (s, 2H, HC]N), 7.71 (s, 4H,
AreCH), 6.84 (s, 4H, AreCH), 6.65 (s, 4H, AreCH), 4.15 (s, 2H, Are-
OH), 1.70 (s, 4H, CH2eCH2), 1.31 (s, 4H, CH2eCH2) and 0.89 (s, 9H, C-
(CH3)3). UVeVis (lmax/(nm), * ¼ shoulder peak): 226, 254, 284 and
326 (in C2H5OH); 249, 272, 594 and 675* (in DMF).
[(LH)2ClCo(4-P)] (9): Color: dark brown, yield: % 70, m. p:
>300  C, Elemental Analysis (C25H27N5O6ClCo, M.A: 587.9 g/mol):
Calculated: C, 51.07; H, 4.63; N, 11.91. Found: C, 51.04; H, 4.59; N,

Please cite this article in press as: A. Kilic, et al., The synthesis and investigation of different cobaloximines by spectroscopic methods, Journal of
Molecular Structure (2018), https://doi.org/10.1016/j.molstruc.2018.03.121
4 A. Kilic et al. / Journal of Molecular Structure xxx (2018) 1e7

11.94%. meff ¼ Dia, LC-MS (Scan ESþ): m/z (%) 587.8 [M]þ. FT-IR (ymax/ 3.2. FT-IR spectroscopy
cm1): 3550 y(OeH), 3040 y(Ar-CH), 2982e2869 y(Aliph-CH), 1721
y(OeH/O), 1618 y(C]N), 1558e1438 y(C]C), 1234 y(NeO) and To obtain particular information on spectroscopic character-
524 y(CoeN). 1H NMR (DMSO-d6, TMS, 300 MHz, d ppm): 19.08 (s, ization of the novel compounds, the FT-IR spectrum of the dioxime
2H, OeH/O), 9.34 (s, 2H, HC]N), 7.74 (s, 4H, AreCH), 6.90 (s, 4H, ligand (2) that was synthesized from monoxime (1) and those of
AreCH), 6.61 (s, 4H, AreCH), 4.27 (s, 2H, AreOH), 2.12 (s, 4H, the corresponding cobaloxime complexes (3e9) were compared to
CH2eCH2), 1.73 (s, 4H, CH2eCH2). UVeVis (lmax/(nm), * ¼ shoulder each other (see Fig. 1 and S1-S3). Due to both y(C]O) and y(C]N)
peak): 224, 252, 286 and 536 (in C2H5OH); 242, 274, 606 and 673* groups, the FT-IR spectrum of the monoxime (1) shows two
(in DMF). stretching vibrations at 1696 and 1617 cm1 which confirm the
formation of the monoxime (1), as expected (see Figure S1). In
addition, a new stretching band is detected at 3368 cm1, which
3. Results and discussion
was due to free y(OeH) group of monoxime (1) compound. The
other stretching frequencies in the FT-IR spectra of (1) have been
3.1. Synthesis and characterization
observed at 3020 cm1 for y(Ar-CH), 2949-2861 cm1 for y(Aliph-
CH), 1594-1511 cm1 for y(C]C), and 1228 cm1 for y(NeO). The
The brown colored monoxime (1) compound was obtained in a
evidence for the formation of dioxime (2) ligand from monoxime
yield of 84% by the reaction of 4-(4-hydroxyphenyl)-2-butanone
(1) was established by disappearance of the y(C]O) peak at
and n-butyl nitrite (C4H9NO2) in anhydrous EtOH and in the pres-
1696 cm1 in monooxime (1) and also the appearance of an azo-
ence of sodium metal at 5  C temperature, according to Scheme 1.
methine y(HC]N) stretching peak with higher frequency observed
The dark brown unsymmetric dioxime ligand (LH2) (2) was ob-
at 1635 cm1 [21,22]. For dioxime (2) ligand (see Fig. 1), the other
tained through the reaction of monoxime (1) with hydroxylamine
characteristic FT-IR peaks were observed at 3378 and 3271 cm1 for
hydrochloride (NH2OH$HCI) in EtOH at reflux temperature and in
the presence of sodium acetate (CH3COONa) (Scheme 1). In the
y(OeH), 3021 cm1 for y(Ar-CH), 2961-2852 cm1 for y(Aliph-CH),
1550-1509 cm1 for y(C]C), and 1233 cm1 for y(NeO). In the FT-
synthesis of both substances, the chemical reactions were sys-
IR spectra of the cobaloxime complexes (3e9), as expected, the two
tematically monitored via TLC chromatography. After the full
oxime y(C]NeOH) stretching vibrations of the dioxime was dis-
characterization of dioxime (2) ligand, the target cobaloxime
appeared, unlike the new characteristics weak deformation peaks
complexes (3e9) were obtained using CoCl2$6H2O and dioxime
were observed at range 1724e1721 cm1 due to the intermolecular
ligand (2) in the presence of different axial neutral bases in EtOH
H-bond y(OeH/O) stretching vibrations that associated with N4-
solvent and in range 72e62% yields, (according to Scheme 1). The
type donor quadridentate Co(III) center and the shifting of y(C]N)
monoxime (1) and dioxime (2) ligand and its cobaloxime com-
and y(NeO) stretches provide support for the formation of coba-
plexes (3e9) were characterized using a combination of various
loxime complexes (3e9) [23]. Furthermore, compared to the
methods including 1H and 13C NMR, FT-IR, UVeVis and LC-MS
dioxime ligand (2) (yC]N ¼ 1635 cm1), stretching peaks of azo-
spectroscopy, melting point measurements, and magnetic suscep-
methine groups y(HC]N) of cobaloxime complexes (3e9) (at range
tibility measurements as well as elemental analysis. All spectro-
1625e1611 cm1) exhibit lower frequency shift, which is the other
scopic results show that monoxime (1) and dioxime (2) ligand and
evidence that the formation of the structurally different cobalox-
its cobaloxime complexes (3e9) were in full agreement with the
ime (3e9) complexes and indicating that the nitrogen atoms of the
proposed molecular structures. However, the different methods
azomethine groups are coordinated to the Co(III) metal ion [24]
and solvent systems were used to obtain single crystals of the
(see Figure S2 and S3). In addition, the FT-IR spectra show that the
monoxime (1) and dioxime (2) ligand and its cobaloxime com-
typical characteristic y(NeO) peaks are detected at 1233 cm1 in
plexes (3e9), unfortunately, we could not obtain single crystals
dioxime ligand (2) and a small frequency shift upon treatment with
suitable for X-ray diffraction studies for all compounds. The
Co(III) center (at range 1235e1230 cm1), which a small frequency
calculated and the found percentages of C, H and N results are in
shift in its position probably because of the formation of Co(III))N
agreement with each other, which supports the proposed molec-
dative bonds in these complexes or owing to the donation of
ular formulas. All compounds are soluble in common organic sol-
electrons from the nitrogen atom into the empty orbitals of the
vents and stable at room temperature and normal pressure, and not
Co(III) center through the four nitrogen atoms [25]. In the low
sensitive to light or air.

Fig. 1. The FT-IR spectra of dioxime (2) ligand.

Please cite this article in press as: A. Kilic, et al., The synthesis and investigation of different cobaloximines by spectroscopic methods, Journal of
Molecular Structure (2018), https://doi.org/10.1016/j.molstruc.2018.03.121
 A. Kilic et al. / Journal of Molecular Structure xxx (2018) 1e7 5

frequency region, new frequencies occurring in the range
532e504 cm1 are attributed to (CoeN) stretching vibrations for
the structurally different cobaloxime (3e9) complexes that are not
observed in the FT-IR of the unsymmetric dioxime (2) ligand [26].
However, the decreases and increases in the strength of the CoeCl
bond may depend on the CoeNaxial bond strength increases in axial
neutral base containing different electron donor/withdrawing
substituents [27]. Appearance of the new bands and the other
differences in the FT-IR spectra proved the formation of dioxime (2)
ligand and its cobaloxime complexes (3e9). Furthermore, the other
stretching frequencies in the FT-IR spectra of dioxime ligand (2) and
its cobaloxime complexes (3e9) are given in the experimental part.
3.3. NMR spectroscopy
The NMR technique has been employed to ascertain the for-
mation of cobaloxime complexes (3e9) from dioxime ligand (2),
which, in turn, synthesized from monoxime (1) and various neutral
bases. The NMR data obviously showed that monoxime (1) and
dioxime ligand (2) with corresponding cobaloxime complexes
(3e9) were successfully synthesized (see Figs. 2 and 3 and S4-S6).
Initially, the 1H NMR spectrum of monoxime (1) was recorded in
DMSO-d6 and D2O resulted in the disappearance of the signal
which the oxime (eOH) signal was observed at 9.62 ppm as singlet
[28,29] (see Figure S4). In addition, in the 1H NMR spectrum of the
monoxime (1), as expected, signal of the (HC]N) proton linked to

Fig. 2. The 1H NMR spectrum of the dioxime ligand (2).

13
Fig. 3. The C NMR spectrum of the dioxime ligand (2).

Please cite this article in press as: A. Kilic, et al., The synthesis and investigation of different cobaloximines by spectroscopic methods, Journal of
Molecular Structure (2018), https://doi.org/10.1016/j.molstruc.2018.03.121
6 A. Kilic et al. / Journal of Molecular Structure xxx (2018) 1e7

the oxime group was observed at 8.46 ppm as a singlet. The peak of
para-OH proton on the benzene ring was observed at 5.56 ppm as a
singlet. Moreover, the 13C NMR data could be analyzed in an anal-
ogous manner to that of the proton and the chemical shift of 13C
NMR peaks supports the formation of the monoxime (1). When the
13
C NMR data were considered, the chemical shifts observed at
d ¼ 208.34 and 155.40 ppm assigned to carbonyl (C]O) carbon and
oxime (C]NOH) carbon, respectively (see Fig. 5S). Moreover, the
other 1H and 13C NMR data of monoxime (1) supported the for-
mation of this compound. The 1H NMR spectra clearly showed that
the deuterium exchangeable signals of the oxime (eOH) peaks
were observed at 10.32 ppm as a singlet for dioxime ligand (2) that
significantly shifted to the lower field in comparison to the mon-
oxime (1) (see Fig. 2). Furthermore, the 13C NMR peaks of two ox-
imes (C]NeOH) group of dioxime ligand (2) observed at 155.62
and 154.61 ppm [30] and the disappearance of the carbonyl (C]O)
signal in the dioxime ligand (2) indicate the converting of the
monoxime (1) to the dioxime ligand (2) (see Fig. 3). Also, the proton
peak of the azomethine (HC]N) group in dioxime ligand (2)
observed at 8.56 ppm, which is shifted to the higher field compared
Fig. 4. The UVeVis spectrum of the [(L1H)2ClCo(4-DAP)] (3) complex in EtOH.
to monoxime (1), due to the conversion of monoxime (1) to the
dioxime ligand (2), as anticipated. In addition, the other 1H and 13C
NMR data of aliphatic and aromatic groups, which are given in the bands were observed at a range of 551e536 nm in C2H5OH and at a
experimental part, supported the formation of the dioxime ligand range of 682e597 nm in DMF solvents. The modifications in shifts
(2). The resonance for the D2O exchangeable intermolecular H- and intensities for the absorption bands supported the coordina-
bond y(OeH/O) protons was observed at a range of tion of the dioxime (2) ligand to the Co(III) ion [33]. The absorption
19.36e17.38 ppm in the 1H NMR spectra of the cobaloxime com- spectra for both the monoxime (1) and dioxime ligand (2) are
plexes (3e9) [31] (see Figs. 6S and 7S), which became very weak almost identical, and are dominated by a strong p/p* absorption
possibly because of the hydrogen bonds. The reason for the transitions observed at range 224e282 nm, with a weaker n/p*
appearance of y(OeH/O) proton peaks at different sites can be absorption transitions observed at range 318e328 nm [34] in
understood from axial groups that are linked to cobaloxime com- C2H5OH or DMF, due to the presence of aromatic rings and func-
plexes. Another decisive event, whereby the signal of the singlet tional oxime (C]NeOH) groups in the structure of two com-
imine (HC]N) proton (at d ¼ 8.56 ppm) of the dioxime ligands (2) pounds. In the UVeVis spectra of cobaloxime complexes, the p/p*
were significantly shifted (at range d ¼ 9.36e8.36) in the different or n/p* ligand-based electronic transition were observed at a
neutral base bound to cobaloxime complexes (3e9), confirming the range of 224e293 nm in C2H5OH and at a range of 232e286 nm in
occurrence of deprotonation and the complex formation via the DMF for cobaloxime complexes (3e9), respectively.
imine nitrogen coordination to the Co(III) center [11]. The signals
for the para-OH proton on the benzene ring for cobaloxime com-
3.5. LC-MS spectroscopy
plexes (3e9) are observed as singlets at a range of 4.52e4.14 ppm,
which were shifted to lower frequencies with respect to the diox-
Formations of the unsymmetric dioxime ligand (LH2) (2) and its
ime ligands (2) due to the electronic and steric effect of the nature
cobaloxime complexes (3e9) were further confirmed by LC-MS
of the axial ligands [32]. The other 1H NMR data of aliphatic and
spectrometer. The calculated and found LC-MS spectra results
aromatic groups supported the formation of the cobaloxime com-
show the expected molecular ion and fragmentation ions with
plexes (3e9), and other NMR data are given in the experimental
appropriate isotope distribution and also the LC-MS data are
part.
consistent with the proposed structures (see Fig. 5 and S9-S11). The
LC-MS spectra of the monoxime (1) and dioxime ligand (2) clearly
3.4. UVeVis spectroscopy
revealed that molecular ion peak corresponding to the monoxime
(1) is detected at m/z ¼ 193.2 amu for [M]þ, and dioxime ligand (2)
To understand the electronic transitions of all compounds, we
is detected at m/z ¼ 208.2 amu for [M]þ (see Figure S9)consecu-
evaluated the UVeVis spectra of the different neutral base bound to
tively, whereas those of the cobaloxime complexes (3e9) were
cobaloxime complexes (3e9) along with that of the dioxime ligand
detected at m/z ¼ 631.1 amu [M]þ for complex (3) (see Fig. 5), at m/
(2) under the same conditions, which were recorded in the
z ¼ 603.8 amu [M]þ for complex (4) (see Figure S10), at m/z ¼ 622.4
200e1100 nm range for comparison (see Fig. 4 and S8) and given in
amu [M]þ for complex (5), at m/z ¼ 602.9 amu [MþH]þ for complex
experimental section. The absorption spectra for all cobaloxime
(6), at m/z ¼ 617.1 amu [MþH]þ for complex (7), at m/z ¼ 644.1 amu
complexes (3e9) are similar for all structure; however, there is a
[M]þ for complex (8), and at m/z ¼ 587.8 amu [M]þ for complex (9)
marked shift in the electronic spectra of Co(III) complexes relative
(see Figure S11), respectively. Additionally, the isotopic patterns for
to that of the dioxime ligand (2). After coordination of the dioxime
all the peaks were in good agreement with the predicted ones [11].
ligand (2) and neutral bases (4-DAP, 4-HP, 4-CP, 4-MP, 4-EP, 4-TBP,
and P) to the Co(III) center, the red or blue shifts in C2H5OH or DMF
solvents of the absorption bands of cobaloxime complexes (3e9) 3.6. Magnetic studies
were compared with that of the dioxime ligands (2). At high con-
centrations, the characteristic Co(III) forbidden DMSO‑d6 transi- The magnetic moments of the cobaloxime complexes (3e9)
tions were observed in the visible region as weakly with low molar containing the various axial neutral bases were measured at
absorption coefficient, which was clearly separated from the other ambient temperature as B.M, where Hg [Co(SCN)4] was used a
ligand-based transitions. These forbidden DMSO‑d6 absorption calibrant. All cobaloxime complexes (3e9) are found to be in

Please cite this article in press as: A. Kilic, et al., The synthesis and investigation of different cobaloximines by spectroscopic methods, Journal of
Molecular Structure (2018), https://doi.org/10.1016/j.molstruc.2018.03.121
 A. Kilic et al. / Journal of Molecular Structure xxx (2018) 1e7
Fig. 5. The LC-MS spectrum of the [(L1H)2ClCo(4-DAP)] (3) complex.
diamagnetic character. The magnetic moment values of cobaloxime
complexes (3e9) found at ~ near zero B. M. for a low spin Co3þ, and
confirm the cobalt in þ3 oxidation state with d6 configuration and
also octahedral geometry and sp3d2 hybridization.
4. Conclusion
In this study, it was the first time we investigated different
cobaloximes with various axial neutral bases for further use in
different applications. The monoxime (1), dioxime ligand (2) and its
cobaloxime complexes (3e9) were obtained and were character-
ized by means of NMR, FT-IR, UVeVis and LC-MS spectrometer,
melting point and magnetic susceptibility measurements as well as
elemental analysis in an easy and efficient strategy. All cobaloxime
complexes (3e9) show absorption bands in the ultraviolet region,
which are similar in overall structure; however, there is a marked
shift in the electronic spectra of Co(III) complexes relative to that of
the dioxime ligand (2). In the FT-IR spectra, we consider the role of
electron donor/withdrawing substituents in axial neutral base on
the CoeB bond to be important. The magnetic moments of the
cobaloxime complexes (3e9) show that they are cobalt centered
being in þ3 oxidation states with d6 configuration and also octa-
hedral geometry with sp3d2 hybridization.
Acknowledgment
This work was supported by the Research Fund of Harran Uni-
versity (HUBAK Projects No: 16098, Sanliurfa, Turkey).
Appendix A. Supplementary data
Supplementary data related to this article can be found at
https://doi.org/10.1016/j.molstruc.2018.03.121.
References
[1] S. Mirra, M. Strianese, C. Pellecchia, V. Bertolasi, G. Monaco, S. Milione, Inorg.
Chim. Acta. 444 (2016) 202e208.
[2] K.L. Brown, Chem. Rev. 105 (2005) 2075e2150.
[3] G. Dutta, B.D. Gupta, J. Organomet. Chem. 696 (2011) 892e896.
[4] S. Kumar, R.W. Seidel, Inorg. Chem. Commun. 27 (2013) 1e4.
[5] S. Hou, H. Yang, B. Cheng, H. Zhai, Y. Li, Chem. Commun. 53 (2017)
Please cite this article in press as: A. Kilic, et al., The synthesis and investigation of different cobaloximines by spectroscopic methods, Journal of
Molecular Structure (2018), https://doi.org/10.1016/j.molstruc.2018.03.121
7
6926e6929.
[6] A. Bhattacharjee, M. Chavarot-Kerlidou, E.S. Andreiadis, M. Fontecave,
M.J. Field, V. Artero, Inorg. Chem. 51 (13) (2012) 7087e7093.
[7] X.L. Hu, B.M. Cossairt, B.S. Brunschwig, N.S. Lewis, J.C. Peters, Chem. Commun.
(2005) 4723e4725.
[8] J.L. Dempsey, J.R. Winkler, H.B. Gray, J. Am. Chem. Soc. 132 (2010) 1060e1065.
[9] P.W. Du, K. Knowles, R. Eisenberg, J. Am. Chem. Soc. 130 (2008) 12576e12577.
[10] T.M. McCormick, B.D. Calitree, A. Orchard, N.D. Kraut, F.V. Bright, M.R. Detty,
R. Eisenberg, J. Am. Chem. Soc. 132 (2010) 15480e15483.
[11] A. Kilic, S. Akdag, E. Aytar, M. Durgun, M. Ulusoy, New J. Chem. 40 (2016)
7901e7910.
[12] A. Kilic, M.V. Kilic, M. Ulusoy, M. Durgun, E. Aytar, M. Dagdevren, I. Yilmaz,
J. Organomet. Chem. 767 (2014) 150e159.
[13] A. Kilic, A.A. Palali, M. Durgun, Z. Tasci, M. Ulusoy, M. Dagdevren, I. Yilmaz,
Inorg. Chim. Acta. 394 (2013) 635e644.
[14] A. Kilic, M. Ulusoy, E. Aytar, M. Durgun, J. Ind. Eng. Chem. 24 (2015) 98e106.
[15] R. Dreos, G. Nardin, L. Randaccio, G. Tauzher, S. Vuano, Inorg. Chem. 36 (1997)
2463e2464.
[16] R. Dreos, G. Nardin, L. Randaccio, P. Siega, Eur. J. Inorg. Chem. (2002)
2885e2890.
[17] S. Kumar, B.D. Gupta, Inorg. Chem. 50 (19) (2011) 9207e9209.
[18] D.L. Jameson, J.J. Grzybowski, D.E. Hammels, R.K. Castellano, M.E. Hoke,
K. Freed, S. Basquill, A. Mendel, W.J. Shoemaker, J Chem. Educ. 75 (1998)
447e450.
[19] A. Earnshaw, Introduction to Magnetochemistry, Academic Press, London,
1968, p. 4.
[20] E. Tas, M. Aslanoglu, A. Kilic, Z. Kara, Trans. Met. Chem. 30 (2005) 758e764.
[21] K.N. Kumar, R. Ramesh, Polyhedron 24 (2005) 1885e1892.
[22] A. Yılmaz, B. Taner, P. Deveci, A.Y. Obalı, U. Arslan, E. Sahin, H.I. Ucan, E. Ozcani
Polyhedron 29 (2010) 2991e2998.
[23] A. Kilic, M. Ulusoy, M. Durgun, E. Aytar, A. Keles, M. Dagdevren, I. Yilmaz,
J. Coord. Chem. 67 (16) (2014) 2661e2679.
[24] A. Kilic, F. Durap, A. Baysal, M. Durgun, J. Inclusion Phenom. Macrocycl. Chem.
67 (2010) 423e429.
[25] J. Song, H. Zhao, Y. Liu, H. Han, Z. Li, W. Chu, Z. Sun, New J. Chem. 41 (2017)
372e376.
[26] I. Babahan, F. Eyduran, N. Orhan, D. Kazar, E. Poyrazoglu-Coban, H. Biyik,
Spectrochim. Acta 121 (2014) 205e215.
[27] A. Panagiotopoulos, K. Ladomenou, D. Sun, V. Artero, A.G. Coutsolelos, Dalton
Trans. 45 (2016) 6732e6738.
[28] Y.S. Li, Q.Z. Yao, Z.H. Wang, J. Cheng, T. Thi, T. Truong, J. Mol. Struct. 1087
(2015) 51e59.
[29] M. Sutradhar, T.R. Barman, S. Ghosh, M.G.B. Drew, J. Mol. Struct. 1037 (2013)
276e282.
[30] E. Tas, M. Aslanoglu, A. Kilic, Z. Kara, J. Coord. Chem. 59 (8) (2006) 861e872.
[31] S. Kumar, R.W. Siedel, Inorg. Chem. Commun. 27 (2013) 1e4.
[32] B.D. Gupta, Veena Singh, R. Yamuna, T. Barclay, W. Cordes, Organometallics 22
(2003) 2670e2678.
[33] A.M. Whyte, B. Roach, D.K. Henderson, P.A. Tasker, M.M. Matsushita, K. Awaga,
F.J. White, P. Richardson, N. Robertson, Inorg. Chem. 50 (2011), 12867e1287.
[34] S. Naskar, S. Naskar, R.J. Butcher, S.K. Chattopadhyay, Inorg. Chim. Acta. 363
(2010) 3641e3646.