Solvent-free synthesis of oxovanadium (V) complexes with isatin base schiff ligands

Article abstract of DOI:10.1080/24701556.2017.1284096

Isatin and its analog are versatile substrates which acts as a precursor for a large number of pharmacologically active compounds, thus having a significant importance in the synthesis of different heterocyclic compounds. This article aims to synthesize the new monooxovanadium(V) complexes with isatin Schiff bases as a ligand. All new compounds structures are characterized and confirmed with spectra analyses.

Full text of DOI:10.1080/24701556.2017.1284096

Inorganic and Nano-Metal Chemistry
ISSN: 2470-1556 (Print) 2470-1564 (Online) Journal homepage: http://www.tandfonline.com/loi/lsrt21
Solven Free Synthesis of Oxovanadium (V)
Complexes with Isatin Base Schiff Ligands
Mohammad Kazem Mohammadi
To cite this article: Mohammad Kazem Mohammadi (2017): Solven Free Synthesis of
Oxovanadium (V) Complexes with Isatin Base Schiff Ligands, Inorganic and Nano-Metal Chemistry,
DOI: 10.1080/24701556.2017.1284096
To link to this article: http://dx.doi.org/10.1080/24701556.2017.1284096
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Date: 16 February 2017, At: 22:17

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Solven Free Synthesis of Oxovanadium (V) Complexes with Isatin Base Schiff Ligands
Mohammad Kazem Mohammadi
Department of Chemistry, Faculty of Science,Ahvaz Branch, Islamic Azad University, Ahvaz,
Iran.
E-mail : mohammadi@iauahvaz.ac.ir
Keywords
Synthesis; Mono oxovanadium ( V) ; Isatin ; Ligands
Abstract
Isatin and its analog, are versatile substrates which acts as a precursor for large number of
pharmacologically active compounds, thus having a significant importance in the synthesis of
different heterocyclic compounds. This article aimes to synthesis of new monooxovanadium( V)
complexes with isatin schiff bases as a ligand.all new compounds structures are scharactrisized
and confirmed with spectra analyses.
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Introduction
Vanadium coordination chemistry constitutes a field of increasing interest and has been the
subject of extensive studies during recent decades by many different authors. A great number of
ligands have been employed in the study of biologically relevant vanadium systems with the aim
of finding a possible correlation between activity and coordination geometry. Diverse aspects
(1–4)
related to its biological and pharmacological activity have been reviewed
.
Vanadium (III, IV and V) has a high affinity for N,O and/or S donor groups. It reacts with many
naturally occurring species, including pyridine carboxylic acids, forming stable complexes of
diverse stoichiometries. Metal complexes of pyridine carboxylic acids and some of their
derivatives have recently received considerable attention as model systems for the design of new
metallopharmaceutical compounds. Furthermore, several vanadium complexes were investigated
as antidiabetic agents, most of them involving vanadium (IV) as the metal center (5–9). Among
others, oxovanadium (IV) associated with picolinate and other related ligands appear as very
promising insulin-mimetic oral active drugs (7–9)
.
It was also determined that vanadium complexes of this bio-ligand are more effective than the
ligand alone in the treatment of diabetes (10). The insulin-like properties of the V(V) dipicolinate
compound, [VO2dipic], originally prepared by Wieghard (11), and its 4-hydroxydipicolinate
derivative, [VO2dipic-OH], have been recently determined (10,12). The structural chemistry of
vanadium (V), like that of other transition metals in high oxidation states, is mainly related to the
oxo complexes. Although a great number of oxo-bridged vanadium (IV and V) and mixed
valence complexes are described in the literature, these compounds are less abundant than those
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of Ti (IV) or Mo (V,VI). Moreover, only few examples of bisoxo- bridged compounds have been
reported (13–14).
(15)
Isatin is an endogenous compound isolated in 1988
and reported to possess a wide range of
(16)
central nervous system activities.
It has also been found as a metabolic derivative of
(16)
adrenaline in humans.
Various derivatives of isatin are known to possess a range of
(17)
pharmacological properties including antiprotozoal activities.
Within the context of enzyme
inhibitors, isatins (also known as 2,3-dioxindoles) have found recent applications in the
(18)
inhibition of cysteine and serine proteases.
Thus isatin is a biologically validated starting
point for the design and synthesis of chemical libraries directed at these targets. (19) , (20)
Various derivatives of isatin are known to adrenaline in possess a wide range of pharmacological
(21)
(22)
properties such as anti-bacterial,
anti-fungal, [22] anti-viral,
anti-HIV,
(24)
(23), anti-leishmanicidal
and cytotoxic activities (25). The aim of the present study is to
determine the complex equilibria of the vanadium metal with isatin sciff bases in solvent free
codition .Spectroscopic methods have been used to confirm of these models of complexation and
to understand the structures of the species formed in aqueous solution.
Results and discussion
The ligands used in this study are shown in Scheme 2. They were prepared by condensing isatin
and aromatic or heterocyclic primary amines in alcoholic solution. Isatin Schiff bases have
been chosen as the Coordinating group for vanadium because it is able to stabilize O_VIV–O–
VV_O bonds (26-30). The organic molecules contain one, two or three tripod tetra dentate binding
sites that are able to coordinate the same number of vanadium atoms (Scheme 2). Bis isatin oxo
vanadium compounds are very hydrophilic and absorb large quantities of water in suspension.
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The vanadium mixed-valence complexes were prepared by mixing the organic ligand with the
appropriate amount of vanadyl sulfate (vanadium (IV) and sodium vanadate (vanadium (V).
In the IR spectrum of the ligands, the bands at 3100 cm-1 are assigned to N–H stretching
frequencies. The carbonyl and azomethine spectral bands are observed at 1630 and 1580 cm-1
respectively. The band at 1250 cm-1respectively corresponds to C-O band. The bands in the
range 1570–1325 cm-1 are difficult to assign due to crowding of bands but sharp bands near to
1450 -1600 cm-1 probably due to the aromatic C-H bands . The IR spectra of the compounds
exhibit significant alterations due to coordination of the bidentate ligand with the metal. The
assignments done are tentative due to crowding of peaks. In compound bis isatin vanadium , a
medium intensity band observed with splittings at 1500 cm-1 is due to newly formed-N=C-C=N-
moiety. The shifting of the C=N band, due to complexation is comparatively less when compared
to that of the ligand and is found at 1580 cm-1. A strong band observed at 1368 cm-1 is assigned
to the band. Strong bands are observed in the range 1510–1420 cm-1. These are attributed to the
aromatic ring vibrations. The typical V=O stretching frequencies in oxo vanadium complexe,
appear as medium strong bands at 962,978 cm-1 bond absorption peaks in the visible region are
obviously moved The stretching vibrations of the V-O and the V-N bond were observed at
453.389 cm-1 .
The 1H NMR spectral, data of free iigands and complexes are shown in follow. As expected, OH
resonances bonding to the aromatic ring and the carboxyl group are absent in the title complexes.
A broad NH and OH (δ 10.12, 8.77 ppm) resonances of the free isatin Schiff bases ligand will be
disappear in the complex structure spectra. indicating coordination through the deprotonated
hydroxyl group. The peaks at 8.2-8.3 ppm and 6.7-6.9 ppm in compIex are attributed to C-H in
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aromatic primary imine and isatin respectively.with different substituents in aromatic primary
imine, the chemical shift of C-H bands will be shifted to up field or down field zone. In 13C
NMR spectra, the peaks that bigger than δ 150 , correspond to C-O , C=N , =C-N bands and δ
120-140 correspond to C-H at Ph in isatin and aromatic imine group .
Experimental
Chemicals
All solvents (Sigma/Aldrich) and chemicals were reagent grade and used without further
purification .Water was deionized (Barnstead D8902 and D8904 cartridges) and distilled
(Corning MP-1 Megapure Still) before use. The yields are for analytically pure compounds with
calculations based on the metal ion, where present.
Instruments
Melting points were determined on the Electro-thermal Melting Point apparatus and were
uncorrected. Infrared spectra were recorded on the Shimadzu-420 infrared spectrophotometer.
1H-NMR and 13C-NMR spectra were recorded in CDCl3 on Brucker 300 MHz spectrometers
(chemical shifts are given in parts per million (PPM)). Elemental analyses (C, H, N) were
performed by the Micro analytical Unit.
General procedure for the synthesis of isatin schiff base derivatives
A mixture of isatin (5 mmol), aromatic or heterocyclic primary amines (5 mmol) are refluxed in
ethanol (50 mL) in the presence of acetic acid as the catalyst for 0.5-2 h. After completion of the
reaction (monitored by TLC), the solvent was removed under reduced pressure and the crude
product was washed with water and recrystallized from ethanol to give pure products.
Some synthesized compounds are compared with those reported in earlier literature [20-24] .
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Solvent free synthesis of new oxo vanadium compounds
A mixture of an [VO(SO4)] (0.25 mmol), isatin Schiff base derivatives (0.5 mmol) were taken in
a dry round-bottomed flask (50 mL). The flask was placed in an oil-bath at a temperature of
110°C fitted with a condenser. The reaction mixture was heated. The reaction was monitored by
TLC till the disappearance of the starting isatin schiff base. On cooling to room temperature (25
°C), the reaction mixture solidified, and product was directly recrystallized from hot methanol to
afforded a solid product that was then isolated by vacuum filtration, washed with cold methanol
and dried overnight in vacuo at RT. Scheme 2.
Some characteristic data for new compounds are given here:
Bis( (Z)-3-(phenylimino)indolin-2-one ) oxovanadium (IV) (scheme 3)
m.p = 285 °C .IR (KBr) cm-1 :3000-3080 C-H(Ph . strech) ,1600 C=N (strech ),1400-1600 C-H
(Ph , bend) , 1100-1310 C-O . 1H NMR (300 MHz, CDCl3) δ 7.5-7.7 (m, 10 H, Ph ) , 6.7-7 (d,
13
8H , Ph). C NMR (300 MHz, CDCl3) δ 126-145 (18 C, Ph), 168 (2C, N=C-O ), 173(2 C=N-
Ph).Elemental analysis for C31H26N4O3V (M.W 533 ). calcld : C 67.27 , H 4.73 , N 10.12 , O
8.67 , V 9.20 . found : C 67.12 , H 4.95 , N 10.24 , O 8.53 , V 9.29 .
Bis( (Z)-3-(4-bromophenylimino)indolin-2-one ) oxovanadium (IV) (scheme 4)
m.p = 281 °C .IR (KBr) cm-1 :3000-3100 C-H(Ph . strech) ,1627 C=N (strech ),1400-1600 C-H
(Ph , bend) , 1125-1331 C-O. 1H NMR (300 MHz , CDCl3) δ 7.5-7.8 (m, 10 H, Ph ) , 6.5-6.8 (d,
13
8H , Ph) . C NMR (300 MHz , CDCl3) δ 125-143 (18 C, Ph), 168 (2C, N=C-O) ,169 (2 C=N-
Ph). Elemental analysis for C31H24Br2N4O3V (M.W 711 ). calcld : C 52.35 , H 3.40 , N 7.88 ,
O 6.75 , V 7.16 , Br 22.47 . found : C 52.44 , H 3.31 , N 7.99 , O 6.55 , V 7.28 , Br 22.29.
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Bis ((Z)-3-(4-fluorophenylimino)indolin-2-one) oxovanadium (IV) (scheme 5)
m.p = 288 °C .IR (KBr) cm-1 :2900-3000 C-H(Ph . strech) ,1616 C=N (strech ),1480-1600 C-H
(Ph , bend) , 1085-1249 C-O . 1H NMR (300 MHz , CDCl3) δ 7.3-7.7 (m, 10 H, Ph ) , 6.5-6.8 (d,
8H , Ph) . 13C NMR (300 MHz , CDCl3) δ 125-140 (18 C, Ph), 164 ( 2C, N=C-O ) , 167 (2 C=N-
Ph). Elemental analysis for C31H24F2N4O3V (M.W 589 ). calcld : C 63.16 , H 4.10 , N 9.50 ,
O 8.14 , V 8.64 , F 6.45 . found : C 63.28 , H 4.35 , N 9.36 , O 7.89 , V 8.71 , F 6.34 .
Bis ((Z)-3-(2,4-dinitrophenylimino)indolin-2-one ) oxovanadium (IV) (scheme 6)
m.p = 294 °C.IR (KBr) cm-1 :2925 C-H(Ph . strech) ,1612 C=N (strech ),1450-1600 C-H (Ph ,
bend) , 1016-1132 C-O . 1H NMR (300 MHz , CDCl3) δ 7.3-7.7 (m, 10 H, Ph ) , 6.5-6.8 (d, 8H ,
Ph) . 13C NMR (300 MHz , CDCl3) δ 125-140 (18 C, Ph), 164 ( 2C, N=C-O ) , 167 (2 C=N-Ph).
Elemental analysis for C31H22N8O11V (M.W 733 ). calcld : C 50.76 , H 3.02 , N 15.28 , O
23.99 , V 6.95 . found : C 50.82 , H 2.93 , N 15.15 , O 23.75 , V 7.12 .
Bis( (Z)-3-(4 - nitro phenylimino)indolin-2-one ) oxovanadium (IV) (scheme 7)
°
m.p= 292 C. IR (KBr) cm-1:2980 C-H(Ph . strech) ,1600 C=N (strech ),1450-1600 C-H (Ph ,
bend) , 1120-1145 C-O . 1H NMR (300 MHz, CDCl3) δ 7.2-7.5 (m,10 H, Ph), 6.6-7.3 (d,8H, Ph)
.13C NMR (300 MHz , CDCl3) δ 123-145 (18 C, Ph), 162 ( 2 C, N=C-O ), 171 (2 C=N-Ph).
Elemental analysis for C31H24N6O7V (M.W 643 ). calcld : C 57.86 , H 3.76 , N 13.06 , O 17.40
, V 7.92 . found : C 57.54 , H 3.61 , N 14.75 , O 23.95 , V 7.22 .
Bis( (Z)-3-(1H-benzo[d]imidazol-2-ylimino) indolin-2-one ) oxovanadium (IV) (scheme 8)
m.p = 276 °C. IR (KBr) cm-1: 3230 N-H ( imidazole , strech ) , 3050 C-H(Ph . strech) ,1580 C=N
(strech ),1450-1600 C-H (Ph , bend) , 1100-1130 C-O . 1H NMR (300 MHz, CDCl3) δ 7.3-7.4
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(m,10 H, Ph -benzo imidazole), 6.5-7.7 (d,8H, Ph-benzo imidazole) .13C NMR (300 MHz ,
CDCl3) δ 122-143 (18 C, Ph), 165 ( 2 C, N=C-O ), 174 (2 C=N-Ph). Elemental analysis for
C33H26N8O3V (M.W 633 ). calcld : C 62.56 , H 4.14 , N 17.69 , O 7.58 , V 8.04 . found : C
62.71 , H 4.25 , N 17.48 , O 7.44 , V 8.19 .
Bis( (Z)-3-( benzo[d]thiazol-2-ylimino) indolin-2-one) oxovanadium (IV) (scheme 9)
m.p = 280 °C. IR (KBr) cm-1: 3075 C-H(Ph . strech) ,1590 C=N (strech ),1450-1620 C-H (Ph ,
bend) , 1110-1130 C-O. 1H NMR (300 MHz, CDCl3) δ 7.3-7.6 (m,10 H, Ph -benzo thiaazole),
6.6-7.3 (d,8H, benzo thiazole) .13C NMR (300 MHz , CDCl3) δ 130-139 (18 C, Ph), 165 ( 2 C,
N=C-O ), 173 (2 C=N-Ph). Elemental analysis for C33H24N6O3S2V (M.W 667 ). calcld : C 59.37
, H 3.62 , N 12.59 , O 7.19 , S 9.61 , V 7.63 . found : C 59.81 , H 3.41 , N 12.43 , O 7.55 , S
9.82 , V 7.46 .
Acknowledgment
The authors will to thanks the Islamic Azad University, Ahvaz Branch, for their supports in this
work .
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Ar
O
N
EtOH
Ar NH2
+
O
O
Reflux
N
N
H
H
Scheme 1: synthesis of isatin schiff bases
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Ar
Ar
N
N
O
VO (SO4)
H
O
N
O
V
MeOH , Reflux
N
O
N
H
H
N
Ar
Scheme 2 : synthesis of new oxovanadyl schiff base complexes
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N
O
V
O
N
N
N
O
(scheme 3)
14
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Br
N
O
O
N
V
N
O
N
Br
(scheme 4)
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F
N
O
O
N
V
N
O
N
F
(scheme 5)
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O2N
NO2
O
N
O
N
V
N
O
N
O2N
NO2
(scheme 6)
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NO2
N
O
O
N
V
N
O
N
NO2
(scheme 7)
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HN
N
N
O
O
N
V
N
O
N
N
NH
(scheme 8)
19
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N
S
N
O
O
N
V
N
O
N
N
S
(scheme 9)
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