A novel reaction of α-carbonyl oxime and amido alcohol: Synthesis, characterization, crystal structure, and thermal studies of an amido alcohol, a new oximino alcohol ligand, and its metal complexes

Article abstract of DOI:10.1080/15533174.2011.591300

In this study, a novel reaction was observed between isonitrosoacetophenone and 1-phenylethanol amine. Acetophenone was used as a starting material to synthesize isonitrosoacetophenone by reaction of acetophenone with n-butyl nitrite in the presence of sodium ethoxide and to synthesize 1-phenylethanol amine by reduction of isonitrosoacetophenone with LiAlH4 in diethyl ether. When the isonitrosoacetophenone reacted with 1-phenylethanol amine, (3E)-3-aza-5-(hydroxyimino)-1,4-diphenylpent-3-en-1-ol monohydrate, a new oximino alcohol ligand and amido alcohol were obtained as associated product interestingly. Four complexes were prepared by treatment of oximino alcohol with metal salts such as Cu^II, Ni^II, Zn^II, and CoII. Amido alcohol was characterized by single-crystal X-ray diffraction, and all complexes were characterized by using spectroscopic techniques and thermogravimetric analysis (TGA). Copyright Taylor &Francis Group, LLC.

Full text of DOI:10.1080/15533174.2011.591300

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Synthesis and Reactivity in Inorganic, Metal-Organic,
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A Novel Reaction of α-Carbonyl Oxime and Amido
Alcohol: Synthesis, Characterization, Crystal
Structure, and Thermal Studies of an Amido Alcohol,
a New Oximino Alcohol Ligand, and its Metal
Complexes
Yunus Kaya a , Gazi Irez a , Hasene Mutlu a & Orhan Buyukgungor b
a Faculty of Arts and Sciences, Department of Chemistry , Uludag University , Bursa,
Turkey
b Faculty of Arts and Sciences, Department of Physics , Ondokuz Mayis University ,
Samsun, Turkey
Published online: 11 Aug 2011.
To cite this article: Yunus Kaya , Gazi Irez , Hasene Mutlu & Orhan Buyukgungor (2011) A Novel Reaction of α-Carbonyl
Oxime and Amido Alcohol: Synthesis, Characterization, Crystal Structure, and Thermal Studies of an Amido Alcohol, a
New Oximino Alcohol Ligand, and its Metal Complexes, Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-
Metal Chemistry, 41:7, 754-762, DOI: 10.1080/15533174.2011.591300
To link to this article: http://dx.doi.org/10.1080/15533174.2011.591300
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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 41:754–762, 2011
Copyright ꢀ Taylor & Francis Group, LLC
C
ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2011.591300
A Novel Reaction of ␣-Carbonyl Oxime and Amido Alcohol:
Synthesis, Characterization, Crystal Structure, and Thermal
Studies of an Amido Alcohol, a New Oximino Alcohol
Ligand, and its Metal Complexes
Yunus Kaya,1 Gazi Irez,1 Hasene Mutlu,1 and Orhan Buyukgungor2
1Faculty of Arts and Sciences, Department of Chemistry, Uludag University, Bursa, Turkey
2Faculty of Arts and Sciences, Department of Physics, Ondokuz Mayis University, Samsun, Turkey
dioximes, imine-oxime ligands, and complexes have been ex-
tensively studied since these structural units are thought to
be involved in a variety of biochemical and industrial pro-
cesses.[4,5]
In this study, a novel reaction was observed between isoni-
trosoacetophenone and 1-phenylethanol amine. Acetophenone
was used as a starting material to synthesize isonitrosoace-
tophenone by reaction of acetophenone with n-butyl nitrite
in the presence of sodium ethoxide and to synthesize 1-
phenylethanol amine by reduction of isonitrosoacetophenone with
LiAlH4 in diethyl ether. When the isonitrosoacetophenone re-
acted with 1-phenylethanol amine, (3E)-3-aza-5-(hydroxyimino)-
1,4-diphenylpent-3-en-1-ol monohydrate, a new oximino alcohol
ligand and amido alcohol were obtained as associated product in-
terestingly. Four complexes were prepared by treatment of oximino
alcohol with metal salts such as CuII, NiII, ZnII, and CoII. Amido al-
cohol was characterized by single-crystal x-ray diffraction, and all
complexes were characterized by using spectroscopic techniques
and thermogravimetric analysis (TGA).
The CuII and NiII complexes have been extensively studied in
recent years.[6,7] During the last decade great attention was given
to the area of multinuclear complexes with extended bridges,[8]
mainly because of the need to gain insight into the electron
transfer pathways in biological systems.[9] The homomultinu-
clear copper complexes of macro cyclic or macro acyclic ligands
have been reported to undergo redox reactions similar to the ac-
tive site in several metalloproteins, and they were also proved to
be efficient catalysts under mild conditions.[10] In order to elu-
cidate the factors that determine the function and activation of
metalloproteins, several works have focused on the understand-
ing of the correlation between the active site of metalloproteins
with their metallocenters.[11]
Keywords amido alcohol, oximino alcohol, reduction
Various methods of amide synthesis were developed. For in-
stance, amide is commonly formed as a product after the reaction
of a carboxylic acid with an amine. Cyclic amide is synthesized
in the Beckmann rearrangement from oximes and amides. It
is also formed by ketones and hydrazoic acid in the Schmidt
reaction.[12] In this work, the synthesis of an oximino alcohol
ligand (3) was performed by the reaction of isonitrosoacetophe-
none (1) with 1-phenylethanol amine (2), and its CuII, NiII, ZnII,
and CoII complexes are explained in detail through this pa-
per. Amido alcohol (4) was obtained as an unexpected product
during the formation of oximino alcohol by a novel method.
The synthesized oximino and amido alcohol were character-
ized by 1H-nuclear magnetic resonance (NMR), 13C-NMR, mass
spectra, infrared spectra, and ultraviolet–visible (UV-VIS) spec-
troscopy. Amido alcohol structure was determined by single-
crystal x-ray diffraction. Elemental analysis, UV-VIS spec-
troscopy, atomic absorption spectroscopy, mass spectra, infrared
(IR) spectra, thermogravimetric analysis (TGA), and magnetic
susceptibility were also used for the characterization of the
complexes.
INTRODUCTION
Oximes are becoming increasingly important as analyti-
cal, biochemical, and antimicrobial reagents. In addition, they
have received much attention due to their use as liquid crys-
tals and dyes. The oximes of various types, such as imine-
oxime, oximino alcohol, α-dioximes, α-keto oximes, amino
oximes, etc., generally form colored soluble or very slightly
soluble chelates with some transition metal salts, which can
be used for different analitical purposes.[1–3] In recent years,
Received 13 October 2010; accepted 21 February 2011.
This work was supported by Uludag University, Scientific Research
Projects Unit grant number 2009/21. The authors are grateful for this
support.
Address correspondence to Yunus Kaya, Faculty of Arts and Sci-
ences, Department of Chemistry, Uludag University, 16059-Bursa,
Turkey. E-mail: ykaya@uludag.edu.tr
754

REACTION OF α-CARBONYL OXIME AND AMIDO ALCOHOL
755
EXPERIMENTAL
but insoluble in hexane and diethyl ether (isolated yield: 0.672 g
(50%), m.p.: 70.9◦C with decomposition). Amido alcohol was
soluble in methanol, ethanol, isopropyl alcohol, and chloroform,
but insoluble in diethyl ether, water, and dichloromethane (iso-
lated yield: 0.108 g (9%), m.p.: 148.3◦C).
Materials and General Methods
All solvents, acetophenone, and metal salts NiCl2·6H2O,
CoCl2·6H2O, CuCl2·2H2O, and Zn(CH3COO)2 were reagent
grade and used without further purification. Isonitrosoacetophe-
none and 1-phenylethanolamine were synthesized according to
procedures described in literature.[13,14] IR spectra (4000–400
cm−1) were recorded on a Thermo Nicolet 6700 FT-IR spec-
Preparation of Complexes
All of the complexes were prepared by the reaction of the ox-
imino alcohol ligand (4) (2 mmol, 0.572 g) in 20 mL ethanol with
the corresponding metal salts (2 mmol; 0.475 g, 0.476 g, 0.341 g,
and 0.367 g, for NiCl2·6H2O, CoCl2·6H2O, CuCl2·2H2O, and
Zn(CH3COO)2 salts, respectively) in 10 mL ethanol at room
temperature over 2 h. (The pH of the reaction mixture was
around 3.5–4.0 and then was adjusted to 5.5–6.0 by adding 1%
NaOH solution, except for the ZnII complex.) The resulting pre-
cipitate was filtered off and washed several times with ethanol
and dried over calcium chloride under vacuum.
trometer using the KBr pellet technique. H- and 13C-NMR
1
spectra of the 1-phenylethanolamine, amido alcohol, ligand,
and its ZnII complex in DMSO-d6 were recorded on a Var-
ian Mercury Plus 400-MHz NMR spectrometer at room tem-
perature using tetramethylsilane (TMS) as internal standard.
The thermogravimetric/differential thermal analysis (TG–DTA)
measurements were obtained using a SII Exstar TG/DTA 6200
thermal analyzer in dry air atmosphere within the temperature
range of 25–1000◦C. The heating rate was 10◦C min−1 and sam-
ple weights ranged from 5 to 10 mg. Electronic spectra were
obtained on a Ati-Unicam UV2 UV-VIS spectrophotometer at
room temperature. Mass spectrum, metal contents in complexes,
and elemental analyses were investigated at the Laboratories
of Scientific and Technological Research Council of Turkey
(TUBITAK). The metal contents of the complexes were de-
termined with atomic absorption spectroscopy. Magnetic prop-
erties were determined by a Sherwood Scientific MK1 model
Gouy magnetic susceptibility balance. Molar conductivities of
10−3 M solutions of the complexes in methanol were measured
on the WTW model inoLab 730 conductivity meter. Melting
points were measured on a Bu¨chi Melting Point B-540 digital
melting point apparatus without being corrected.
X-Ray Structure Determination
Intensity data for the title compound was collected using
a STOE IPDS 2 diffractometer with graphite-monochromated
(Mo-Kα radiation, λ = 0.71073 Å) at 120 K. The structure
was solved with SHELXS-97[15] and refined using SHELXL-
97.[16] All the nonhydrogen atoms were refined with anisotropic
displacement parameters. All hydrogen atoms were included
using a riding model in idealized positions. The details of data
collection, refinement and crystallographic data are summarized
in Table 1.
RESULTS AND DISCUSSION
Synthesis of Isonitrosoacetophenone (1) and
1-Phenylethanol Amine (2)
Synthesis
Isonitrosoacetophenone (1) and 1-phenyl ethanolamine (2)
were obtained as mentioned in the literature.[13,14] Oximino al-
cohol ligand (3) was synthesized by reaction of isonitrosoace-
tophenone with 1-phenylethanol amine as mentioned in mod-
erate yield (50%). After separating the oximino alcohol ligand
from the reaction mixture, the filtrate was evaporated and then
the oily product was recrystallized, so the unexpected product,
amido alcohol (4), was obtained at very low yield (9%). Stable
solid metal complexes were synthesized by interaction of metal
salts with the oximino alcohol ligand in ethanol (yields between
72 and 86%).
Isonitrosoacetophenone was synthesized by reaction of ace-
tophenone with n-butyl nitrite in presence of sodium ethox-
ide,[13] and 1-phenylethanol amine was obtained by reduction
of isonitrosoacetophenone with LiAlH4 in diethyl ether.[14]
Synthesis of (3E)-3-Aza-5-(hydroxyimino)-1,4-
diphenylpent-3-en-1-ol Monohydrate, Oximino Alcohol
(3), and Amido Alcohol (4)
A solution of 1-phenylethanolamine (5 mmol, 0.685 g amine
in 10 mL ethanol) was added dropwise to a solution of isoni-
trosoacetophenone (5 mmol, 0.745 g in 20 mL ethanol) for 20
min at room temperature. After the reaction mixture had been
stirred for 5 h at the same temperature, the solution was left
overnight at 0◦C. The yellow crystallized product (3E)-3-aza-5-
Crystal Structure Description
Analytical data (C, H, and N contents) are consistent with the
(hydroxyimino)-1,4-diphenylpent-3-en-1-ol monohydrate, ox- proposed empirical formulas, also confirmed by single crystal
imino alcohol, was filtered, washed with diethyl ether, and dried x-ray diffraction analysis for amido alcohol. The molecular
in air. Filtrate was removed by evaporation. The oily product was structure of amido alcohol with the atom labeling is shown in
dissolved in 1:1 ethanol:water and precipitated. The obtained Figure 2, and selected bond lengths and angles together with
crystalline material (amido alcohol) was filtered, washed with hydrogen bonding geometry are listed in Tables 2 and 3. The
diethyl ether, and dried in air (Figure 1). Oximino alcohol was C(7)-O(1) distance of 1.250 Å is consistent with a carbonyl C=O
soluble in methanol, ethanol, isopropyl alcohol, and chloroform, bonding. This value is higher than expected due to the strong

756
Y. KAYA ET AL.
FIG. 1. The illustration of the synthesis of the oximino alcohol ligand and amido alcohol.
intermolecular hydrogen bond. The molecular structure of
amido alcohol has two intermolecular hydrogen bondings: One
intermolecular hydrogen bond, the length of which is 2.14 Å, is
between the oxygen atom O(1) of carbonyl group and hydrogen
atom of an amide group belonging to neighbor molecule
N(1)-H. Another intermolecular hydrogen bond, the length of
which is 1.95 Å, also exists between carbonyl oxygen O(1)
and the alcohol hydrogen of the other neighboring molecule
O(2)–H.
Infrared Spectra
In general, the complexes exhibit very comparable IR behav-
ior with similar structure.[17-19] Relevant bands are given later,
in Table 5. In the IR spectrum of oximino alcohol ligand (3),
the O-H, C=Nimine, C=Noxime, and N-O stretching vibrations are
observed at 3198, 1633, 1597, and 1016 cm−1, respectively. The
band at 1112 cm−1 corresponds to the alcoholic C–O stretch-
ing vibration of the synthesized ligand. Additionally, the peak,
centered at around 2612 cm−1 and very broad, indicates an
FIG. 2. The crystal structure of amido alcohol (color figure available online).

REACTION OF α-CARBONYL OXIME AND AMIDO ALCOHOL
757
TABLE 1
Crystallographic data for amido alcohol
TABLE 3
Hydrogen bonding geometry for amido alcohol
Empirical formula
Mr
T (K)
Diffractometer
Radiation, λ (Å)
Crystal system
V (Å3)
C15H15NO2
241.28
293 (2)
Stoe IPDS-II
Mo Kα / 0.71073 Å
Ortorombic
2631.58(19)
8
D−H···A
D−H (Å) H···A (Å) D····A (Å) (D−H···A) (◦)
N1-H4···O1i
0.81(3) 2.14(3) 2.902(3)
158(3)
169(3)
O2-H15···O1ii 0.84(3) 1.95(4) 2.785(3)
Symmetry codes: (i) x – 1/2, y, –z + 3/2; (ii) x – 1/2, –y + 1/2, –z
+ 1.
Z
oxime nitrogen coordinate to the metal ion.[17,18] Besides, the
C-O stretching vibrations in the CuII, NiII, and CoII complexes
are observed at 1135–1144 cm−1. The bands shift to higher
wavenumber by 23–29 cm−1 due to O–metal coordination, and
this result indicates that the alcohol loses its proton.[19] In the
Unit cell dimensions
a (Å)
b (Å)
c (Å)
α (◦)
β (◦)
γ (◦)
9.1557(3)
29.1108(11)
9.8735(5)
90.00
90.00
90.00
ZnII complex, there exists a C-O stretching band at 1118 cm−1
.
This result indicates that the alcohol doesn’t lose its proton.
This situation is also supported by 1H-NMR. The N-O band of
the ZnII complex is observed at the same wavenumber as the
ligand’s band, so it can be considered that the oxime group of
ligand may lose its proton and may bond from the oxygen atom
to the metal ion in the ZnII complex. The carbonyl peak around
1651 cm−1 indicates that acetate anion was successfully incor-
porated into the complex. The presence of a broad absorption
band centered at 3453–3500 cm−1 in the IR spectra of the ox-
imino alcohol ligand and NiII, CoII, and CuII complexes (5–7)
is evidence of the presence of water molecules. The O-H char-
acteristic peak belonging to NiII, CoII, and CuII complexes was
overlapped by water molecules, so O-H peaks belonging to the
oxime couldn’t be seen. This interpretation is also supported by
IR, NMR, elemental analyses, and thermogravimetric analysis
(Tables 4–6).
Dc (mg m−3
)
1.218
θ range (◦)
1.40–25.69
–11/11, –35/35, –11/11
2489
1535
0.1233
Index range (h, k, l )
Reflections collected (I > 2α)
Independent reflections (Rint)
R
wR
0.1157
1.143
Goodness of fit on F2
intra- or intermolecular hydrogen bond in the ligand. The
C=Nimine, C=Noxime, and N-O stretching vibrations in the com-
plexes are observed at 1617–1626, 1594–1597, and 1020–1064
cm−1, respectively. The υ(C=N) bands shift to a lower region
when the spectra of the complexes are compared with that of the
oximino alcohol ligand. These results indicate that the imine and
In the IR spectrum of amido alcohol (4), the C=O, N–H, and
O–H stretching vibrations are observed at 1612, 3308, and 3405
cm−1, respectively.
TABLE 2
NMR Spectra
1
The H- and 13C-NMR spectra of the compounds (1), (2),
Selected bond lengths and angles for amido alcohol
(3), (4), and (8) are recorded using DMSO-d6 as the solvent
Bond lengths (Å)
Bond angles (◦)
1
(Table 6). The H- and 13C-NMR spectral studies give impor-
1
tant clues concerning the structures. H-NMR spectrum of the
C1−C2
1.380(4)
1.387(5)
1.374(6)
1.482(4)
1.250(3)
1.329(3)
1.457(4)
1.521(4)
1.423(3)
1.507(4)
1.380(4)
1.373(5)
1.378(5)
C1-C2-C3
120.1(4)
123.3(3)
119.8(4)
118.1(3)
120.4(2)
121.5(3)
122.6(2)
111.7(2)
105.9(2)
108.0(2)
119.0(2)
109.1(15)
116.0(2)
isonitrosoacetophenone (1) clearly demonstrates the presence of
a C=N–OH environment at 11.73 ppm, but this proton cannot
be observed in (3) and (8).[20] At the same time, the alcoholic
OH proton of the ligand doesn’t appear, so we think that O-H
peaks are shielded by the H2O peak. The azomethine (CH=N)
protons for the compounds (1), (3), and (8) appear at 8.01, 8.00,
and 8.03 ppm, respectively. When the values of the chemical
shifts for the compounds (1), (3), and (8) are compared, it can
be seen that there is not any great difference among them. The
appearance of a signal at 5.51 and 8.11 ppm may be assigned
to the existence of –OH group of (4) and (8), respectively. The
result for the ZnII complex (8) shows that the alcohol group of
the oximino alcohol ligand doesn’t lose its proton and bonds
C2−C3
C2-C1-C7
C3-C4-C5
C6-C1-C7
O1-C7-C1
O1-C7-N1
C7-N1-C8
N1-C8-C9
O2-C9-C8
C9-O2-H15
C7-N1-H4
N1-C8-H3
C11-C10-C15
C3−C4
C1−C7
C7−O1
C7−N1
C8−N1
C8−C9
C9−O2H
C9−C10
C10−C15
C14−C15
C13−C14

758
Y. KAYA ET AL.
TABLE 4
Some analytical data and physical properties of the ligand, amido alcohol, and complexes
Elemental analyses (%) found (calculated)
ꢀM
(Ω−1 cm2 m.p.
Formula
weights
Yield
(%)
Compound
Color
mol−1
)
(◦C )
(g mol−1
)
C
H
N
M
H2L.H2O (3)
Yellow
White
Green
Brown
6.3
—
3.7
5.3
19.1
5.1
70.9d
148.3
50
9
82
76
86
72
286.3
241.3
379.5
379.7
750.6
391.7
66.42 (67.08) 6.02 (6.29) 9.41 (9.79)
69.67 (69.70) 5.87 (5.80) 5.73 (5.80)
50.72 (50.51) 4.29 (4.47) 7.58 (7.40) 15.25 (15.55)
50.76 (50.51) 4.19 (4.47) 7.51 (7.40) 14.15 (15.55)
51.68 (51.23) 4.22 (4.27) 7.24 (7.47) 16.17 (16.93)
55.17 (55.21) 4.64 (4.60) 7.60 (7.21) 16.47 (16.62)
—
—
Amido alcohol (4)
NiHLCl·H2O (5)
CoHLCl·H2O (6)
245.0d
185.6d
117.4d
129.1d
Cu2(HL )2Cl2·H2O (7) Green
ZnHLCH3COO (8)
Yellow
d Decomposition point.
TABLE 5
Characteristic IR bands (cm−1) of the ligand, amido alcohol, and complexes
Compound
ν(NH2)
ν(OH)
ν(OH2) ν(CH)arom ν(CH)aliph
ν(C=O)
ν(C=N)
ν(C–O) ν(NO)
Isonitrosoacetophenone (1)
1-Phenyl ethanolamine (2)
H2L·H2O (3)
—
3272br
2700br
3198s, 2612br 3500br
—
—
3011m
3028w
3058w
3055w
3052w
3053w
3059m
3060w
2894m
2918w
2920w
2935w
2917w
2924w
2933 w
2925w
1678s
—
—
1612s
—
—
1599s
—
1633s 1597s
—
1618s 1596m
1625m 1596m
1626s1597s
1617m 1594s
—
985s
—
1016s
—
1041m
1064m
1036w
1020m
3387s, 3358m
1065s
1112s
1073s
1135s
1145s
1138s
1118s
—
Amido alcohol (4)
NiHLCl·H2O (5)
ν (NH) 3308s
3405s
—
—
—
3403br
—
—
—
—
—
3405br
3453br
3430br
—
CoHLCl·H2O (6)
Cu2(HL )2Cl2·H2O (7)
ZnHLCH3COO (8)
—
1651m
s: Strong, m: medium, w: weak; br: broad.
TABLE 6
1H- and 13C-NMR spectral data (ppm) of the ligand, amido alcohol, and ZnII complex
1H-NMR spectra
Compounds
O–H
C–Halde
C–Harom
C–H
CH2
N–H
C–H3
Isonitrosoacetophenone (1) 11.73 (s, 1H) 8.01 (s, 1H) 7.51–7.95 (m, 5H)
1-Phenyl ethanolamine (2) 2.22 (s, 1H) 7.25–7.37 (m, 5H) 4.65 (m, 1H) 2.95 (m, 2H) 2.22 (s, 2H)
Not observed 8.00 (s, 1H) 7.19–7.96 (m, 10H) 4.43 (m, 1H) 2.62 (m, 2H)
5.51 (d, 1H) 7.20–7.82 (m, 10H) 4.76 (m, 1H) 3.36 (m, 2H) 8.49 (t, 1H)
—
—
—
—
H2L.H2O (3)
Amido alcohol (4)
ZnHLCH3COO (8)
—
—
8.11 (s, 1H) 8.03 (s, 1H) 7.23–7.96 (m, 10H) 4.41 (m, 1H) 2.53 (d, 3H)
—
1.90(s,3H)
13C-NMR spectra
C=O
168.7
—
—
166.8
177.7
RC = NRı
—
—
189.4
—
H-C = NOH
148.2
—
Ph(C–H)
C–H
—
74.3
74.7
71.6
75.6
CH2
—
49.2
50.5
48.1
48.1
C-H3
—
—
—
—
Isonitrosoacetophenone (1)
1-Phenyl ethanolamine (2)
H2L.H2O (3)
Amido alcohol (4)
ZnHLCH3COO (8)
128.0–134.1
125.9–142.5
126.3–144.7
126.4–144.2
126.0–144.2
148.1
—
147.8
190.7
22.3

REACTION OF α-CARBONYL OXIME AND AMIDO ALCOHOL
759
TABLE 7
Mass spectra data, UV-VIS spectra data, and magnetic moment measurements of the ligand, amido alcohol, and complexes
Compound
MS (ESI), m/z
λmax, nm
µeff (B.M.)
H2L·H2O (3)
269.1(100), 185.1(60), 172.0(10), 120.1(20)
241.8(40), 223.7(100), 104.8(10)
381.0(5), 379.1(20), 321.0(10), 282.1(20), 223.9(100), 162.8(25)
379.9(10), 321(60), 256.0(100), 142.8(40), 108.8(25)
753.8(10), 749.0(45), 521.8(15), 427.4(25), 282.1(100), 126.8(20)
392.0(5), 391.2(15), 324.9(15), 268.9(100), 223.9(20), 149.8(50), 119.9(45)
208, 256, 268, 341
—
—
2.99
4.04
1.19
Dia
Amido alcohol (4)
NiHLCl·H2O (5)
CoHLCl·H2O (6)
Cu2(HL)2Cl2·H2O (7)
ZnHLCH3COO (8)
—
208, 256, 275, 352, 399, 630
207, 256, 280, 354, 409
210, 256, 270, 350, 428, 714
205, 256, 272, 310, 397
from the oxygen atom to the metal ion. At the same time, the imine π–π∗ and n–π∗ transitions shift to longer wavelengths
CH3 protons at 1.90 ppm demonstrate that acetate anion partic- after complexation, so this confirms the imine nitrogen is coor-
ipates in the ZnII complex. Aromatic C–H protons are observed dinated to the metal atom.[23] NiII and CuII complexes reveal a
at 7.20–7.96 ppm in all of the structures. The N-H proton ap- less intense shoulder at 630 nm (ε = 130 L mol−1 cm−1) and 714
pears at 8.49 ppm in compound (4). In the 13C-NMR spectrum nm (ε = 470 L mol−1 cm−1), assigned to d–d transitions of the
of (4), carbonyl carbon is observed 166.8 ppm and the signals of metal ions, respectively. The weak d–d transition couldn’t be ob-
the Caromatic carbon are observed at 126.4–144.2 ppm.[21] In the served in the CoII complex. Because the d–d transition may shift
13C-NMR spectrum of compound (3), the signals of the carbon the UV region, this band may remain below the charge transfer
atoms of azomethine groups appear at 189.4 and 148.1 ppm. transition. Five coordinated CuII complexes showing absorp-
The signals of the Caromatic carbon are observed at 126.5–144.7 tion in the 588–769 nm region approximate a square pyramidal
ppm. The peaks of C-H and C-H2 appear at 74.7 and 50.5 ppm, geometry, while complexes with a trigonal bipyramidal geom-
respectively.[22] In compound (8), the signal of the carbon atom etry show absorption bands in the 685–952 nm region, with
of imine group appears at 190.7 ppm. This shows that the lig- highest absorption intensities in the range 666–877 nm.[24,25]
and bonds from the imine nitrogen atom to the metal ion in the
ZnII complex. Carbonyl carbon and CH3 carbon are also seen at
177.7 and 22.3 ppm. It is concluded that acetate anion partici-
pates in the ZnII complex. The 1H- and 13C-NMR spectral data
support the proposed structures and indicate the formation of the
amido alcohol, oximino alcohol ligand, and its ZnII complex.
Mass Spectra
The mass spectra (electrospray ionization, ESI) of oximino
alcohol ligand and amido alcohol exhibit a molecular ion at m/z
269.1 (268.3) [M-H2O]+, which indicates the formation of the
ligand, and a molecular ion at m/z 241.8 (241.3) [M]+, which
indicates the formation of the amido alcohol. The molecular
ion peaks appear at (m/z, ESI) 379.1(378.0) [M]+, 379.9(379.0)
[M]+, 749.0(748.0) [M]+, and 391.2(390.0) [M]+ for the NiII,
CoII, CuII, and ZnII complexes, respectively (Table 7).[6] There
are two or more isotopes for Ni, Cu, Zn, and chlorine, so mass
spectra of these complexes have been observed with isotopic
effects. For instance, there are tree isotopes of copper and two
isotopes of chlorine, with 63Cu (69%) and 35Cl (76%) being the
most abundant isotopes, so two peaks 749.0 (45) and 753.8(15)
are observed in the CuII complex.
Electronic Spectra
The electronic spectra of the ligand and complexes are
recorded in chloroform at room temperature (Table 7). Elec-
tronic spectral data show π–π∗ transitions relating to the ben-
zene ring at 205–256 nm, imine π–π∗ transition at 268–280 nm,
and imine n–π∗ transition at 310–354 nm. In the complexes,
FIG. 3. DTA and TG curves of oximino alcohol (3) and its NiII complex (5)

760
Y. KAYA ET AL.
TABLE 8
Thermal decomposition of the ligand and complexes
Mass loss (%) Residue (%)
Temperature
range (◦C)
found
found
(calculated)
Leaving Decomposition
group product
Compound
Step
DTAmax. (◦C) (calculated)
H2L·H2O (3)
1
2
3
4
1
2
3
1
2
3
1
2
3
4
1
2
3
28–76
56(+)
6.10 (6.25) 93.90 (93.71) H2O
H2L
(L:C16H16N2O2)
77–192
193–422
423–647
32–101
102–288
289–461
46–124
125–208
209–518
51–95
96–202
203–392
393–594
49–218
219–442
443–530
126(–), 190(–) 15.32
340(–), 402(–) 50.56
559(–), 593(–) 26.12
1.90 (0)
H2L
—
NiHLCl·H2O (5)
83(+)
4.12 (4.74) 95.88 (95.26) H2O
NiHLCl
233(–), 274(–) 35.28
395(–), 401(–) 41.04
19.56 (19.76) HLCl
4.25 (4.74) 95.75 (95.26) H2O
35.71
20.02 (19.76) HLCl
2.13 (2.40) 97.87 (97.60) H2O
24.81
NiO
CoHLCl
CoHLCl·H2O (6)
Cu2(HL)2Cl2·H2O (7)
92(+)
186(–)
362(–), 375(–) 40.02
CoO
Cu2(HL )2Cl2
78(+)
122(–)
267(–), 300(–) 24.57
486(–)
140(–)
415(–)
483(–)
28.70
20.28 (21.20) 2 HLCl
CuO
ZnHLCH3COO (8)
17.17 (15.08) 82.83 (84.92) CH3COO ZnHL
38.59
25.08
19.16 (20.72) HL
ZnO
(+) : endothermic, (–): exothermic.
FIG. 4. The schematic illustration of related metal complexes.

REACTION OF α-CARBONYL OXIME AND AMIDO ALCOHOL
761
The electronic spectrum of the CuII complex has agreed with
a square pyramidal structure, which is confirmed by structural
studies.[26] Additionally, d–d transition of the metal ion is prob-
amine. We reported the oximino alcohol’s complexes with the
appropriate transition metal ions such as CuII, NiII, ZnII, and
CoII. Spectroscopic measurements and magnetic moment stud-
ies showed that NiII, CoII, and ZnII complexes have high-spin
distorted tetrahedral configuration, CuII complexes have square
pyramidal configuration, and the CuII complexes possess an-
tiferromagnetic properties by strong intramolecular antiferro-
magnetic spin exchange interaction, so we suggested a dinuclear
structure for the CuII complex. These complexes may serve as
models of relevance to bioinorganic chemistry such as met-
alloenzymes. The infrared, UV-VIS, elemental analyses, and
magnetic moment studies suggest that the azomethine nitrogen,
oxime nitrogen, and deprotonated alcoholic oxygen atom of the
oximino alcohol ligand are coordinated and covalently bonded
to metal atoms in the NiII, CoII, and CuII complexes and the
azomethine nitrogen, deprotonated oxime oxygen, and alcoholic
oxygen atom of the oximino alcohol ligand are coordinated and
covalently bonded to metal atoms in the ZnII complex (Figure
4). Thus, the oximino alcohol ligand behaves as tridentate.
It was observed that amido alcohol was obtained as asso-
ciated product during the reaction. This structure was charac-
terized with spectroscopic and single-crystal x-ray diffraction
methods. In conclusion, we determined that the reaction be-
tween isonitrosoacetophenone and 1-phenyl ethanolamine was
very novel.
3
ably due to the 3A2 → T2 (F) transition of tetrahedral geometry
for NiII complex.[27] The spectra of all the complexes show an
intense band at ∼397–428 nm (ε = 1.08–1.96 × 104 L mol−1
cm−1), which can be assigned to charge transfer (CT) transition
of tetrahedral geometry.[28]
Magnetic Susceptibility and Molar Conductance Studies
The magnetic moments of the complexes are investigated at
room temperature (Table 7). Magnetic susceptibilities of NiII,
CoII, and CuII complexes are measured as 2.99, 4.04, and 1.19
B.M., respectively. As expected, the ZnII complex doesn’t show
any magnetism. It is obvious that the CuII complex possess anti-
ferromagnetic properties at room temperature, shown by strong
intramolecular antiferromagnetic spin exchange interaction as
reported previously for di- and trinuclear CuII complexes with
oximate bridged ligands.[29,30] The measurements of the mag-
netic susceptibility of the complexes having d8 and d7 configura-
tions show that the complexes may have tetrahedral or tetragonal
structures for NiII and CoII complexes, and these results are well
adjusted with the previous studies.[28,31]
The molar conductance values of the synthesized oximino al-
cohol ligand and its CuII, NiII, ZnII, and CoII complexes are in a
range from 3.7 to 19.1 ꢁ−1 cm2 mol−1 in methanol solutions, in-
dicating the nonelectrolyte nature of these compounds.[32] These
values provide some indication to support our proposed struc-
tural conformation for complexes.
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