Synthesis of some transition metal complexes of ligands derived from 5-phenyl-2,3-dihydro-2,3-furandione

Article abstract of DOI:10.3184/030823408X318307

A series of amide ligands was prepared by the reactions of 5-phenyl-2,3-dihydro-2,3-furandione and aromatic amines. The ligands reacted with Cu(II) and Ni(II) ions to yield mononuclear complexes. The ligands and complexes were characterised by elemental analyses, mass, FTIR, UV-vis, ¹H NMR and ¹³C NMR spectral studies, as well as magnetic moment, AAS and conductance measurements as appropriate.

Full text of DOI:10.3184/030823408X318307

256 RESEARCH PAPER
MAY, 256–259
JOURNAL OF CHEMICAL RESEARCH 2008
Synthesis of some transition metal complexes of ligands derived from
5-phenyl-2,3-dihydro-2,3-furandione
Esvet Akbas*, Mehmet Sonmez, Metin Celebi and Furgan Aslanoglu
Department of Chemistry, Faculty of Sciences, University of Yuzuncu Yil, 65080, Van, Turkey
A series of amide ligands was prepared by the reactions of 5-phenyl-2,3-dihydro-2,3-furandione and aromatic
amines. The ligands reacted with Cu(II) and Ni(II) ions to yield mononuclear complexes. The ligands and complexes
1
were characterised by elemental analyses, mass, FTIR, UV-vis, H NMR and 13C NMR spectral studies, as well as
magnetic moment, AAS and conductance measurements as appropriate
Keywords: IXUDQGLRQHꢀꢁWUDQVLWLRQꢁPHWDOꢁFRPSOH[HVꢀꢁDPLGHꢀꢁV\QWKHVLV
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transition metals.
Result and discussion
The amide derivatives 2a–cꢁZHUHꢁSUHSDUHGꢁvia reaction of 5-
SKHQ\OꢄꢂꢀꢃꢄGLK\GURꢄꢂꢀꢃꢄIXUDQGLRQHꢁꢆ1ꢇꢁZLWKꢁDURPDWLFꢁDPLQHVꢁ
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conditions. Reaction of furandione (1) and aromatic amines
in absolute chloroform at room temperature for 72 h gave
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ZHUHꢁREWDLQHGꢁLQꢁJRRGꢁ\LHOGꢉ
amines,11-13
ꢁ
K\GUD]LGHVꢀ12 carbodiimides,14 acetanilides15
and azomethines16 under different conditions. Most of these
V\QWKHVLVHGꢁ FRPSRXQGVꢁ LQꢁ JHQHUDOꢁ DUHꢁ ZHOOꢁ NQRZQꢁ IRUꢁ WKHLUꢁ
potential biological activities.8,17ꢁ :KHQꢁ ꢂꢀꢃꢄGLK\GURꢄꢂꢀꢃꢄ
IXUDQGLRQHVꢁ UHDFWꢁ ZLWKꢁ DURPDWLFꢁ RUꢁ KHWHURF\FOLFꢁ DPLQHVꢁ
such as aniline, p-toluidine, pꢄDQLVLGLQHꢀꢁ ꢂꢄS\ULG\ODPLQHꢁ RUꢁ
ꢂꢄS\ULPLG\ODPLQHꢀꢁ DUR\ODPLGHVꢀꢁ ZKLFKꢁ DUHꢁ EꢄGLFDUERQ\Oꢁ
compounds, are obtained.18
7KHꢁ ȕꢄGLFDUERQ\Oꢁ FRPSRXQGVꢁ VXFKꢁ DVꢁ GLEHQ]R\OPHWKDQHꢀꢁ
DFHW\ODFHWRQꢁ RUꢁ DFHWRDFHWDWHꢁ DUHꢁ FRPPRQO\ꢁ XVHGꢁ LQꢁ RUJDQLFꢁ
FKHPLVWU\ꢉ These compounds constitute an important ligand
class in terms of their distinctive structural properties and high
V\QWKHWLFꢁXWLOLW\ꢉꢁ7KH\ꢁH[LVWꢁLQꢁWZRꢁWDXWRPHULFꢁIRUPVꢉ19,20 Metal
FRPSOH[HVꢁ RIꢁ ȕꢄGLFDUERQ\Oꢁ FRPSRXQGVꢁ DUHꢁ RIꢁ FRQVLGHUDEOHꢁ
commercial interest. These metal complexes are used in the
production of laser devices,21 as NMR shift reagents and in
DQDO\WLFDOꢁFKHPLVWU\ꢉ 22
According to FTIR and 1H NMR spectra, tautomerisation in
WKHꢁOLJDQGVꢁDSSHDUHGꢁLQꢁWKHꢁFDUERQ\OꢁJURXSVꢁꢆ6FKHPHꢁꢂꢇꢉ
The FTIR spectrum of 2a VKRZHGꢁ DQꢁ DEVRUSWLRQꢁ EDQGꢁ DWꢁ
3226–3220 cm-1 ꢆK\GUR[\OꢁIXQFWLRQꢇꢁDVꢁZHOOꢁDVꢁWZRꢁFDUERQ\Oꢁ
1
absorption bands at 1698 and 1584 cm-1. In the H NMR
spectra of 2a, the signal at Gꢁ ꢊꢂꢉꢋꢌꢁ ZDVꢁ Dꢁ EURDGꢁ VLQJOHWꢁ
GXHꢁ WRꢁ WKHꢁ K\GUR[\Oꢁ SURWRQꢀꢁ ZKLFKꢁ XQGHUJRHVꢁ NHWRꢄHQROꢁ
WDXWRPHULVDWLRQꢉꢁ7KHꢁNHWRꢄꢁDQGꢁHQROꢄIRUPVꢁDUHꢁLQꢁHTXLOLEULXPꢀꢁ
although the enol form predominates here. The resonances
O
X
O
X
X
H
N
O
O
O
H2
N
+
O
Ph
H2N
Y
Ph
Ph
O
O
O
1
Y
Y
X
H
OH
O
N
Ph
O
2
Y
X=-COOCH3 (a), -COOC2H5 (b), H (c)
Y= H (a), H (b), NO2 (c) [11]
Scheme 1
H
H
X
X
O
O
X
O
O
H
N
O
O
H
N
N
Ph
Ph
Ph
OH
O
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Y
Y
2a, b, c
Scheme 2
* Correspondent. E-mail: esvakbas@hotmail.com

JOURNAL OF CHEMICAL RESEARCH 2008 257
PD\ꢁEHꢁGXHꢁWRꢁ0±2ꢉ25-27 The FTIR spectra of the complexes
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3435–3595 cm-1ꢁ DUHꢁ GXHꢁ WRꢁ WKHꢁ 2+ꢁ IUHTXHQF\ꢁ RIꢁ ZDWHUꢁ RIꢁ
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HOHPHQWDOꢁDQDO\VHVꢉ
RIꢁ K\GUR[\Oꢁ SURWRQVꢁ JHQHUDOO\ꢁ RFFXUꢁ GRZQ¿HOGꢁ ꢆGa7.5–4).
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range, at about Gaꢊꢂ±ꢊꢍꢀꢁEHFDXVHꢁRIꢁLQWUDPROHFXODUꢁK\GURJHQꢁ
bonding.23 The singlets at 8.87 and 8.82 ppm are due to
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7KHꢁVSHFWUDꢁZHUHꢁUHFRUGHGꢁLQꢁ'0)ꢁDVꢁVROYHQWꢉ
NH OH tautomerisation. The singlets at 7.32 and 4.00 ppm
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The 13C NMR spectrum of 2a revealed signals at G 187.53,
181.77 (C=O), and 96.02, 54.65 ppm (–CH and -CH3 groups)
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molecular ion peak at m/e 325.0.
The UV-vis spectra of Ni(II) complexes recorded herein are
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3
642-666 nm due to A2g ĺꢀ3T2g(Ȟ1) and the other 404–428
nm for 3A2g ĺꢀ3T1g(Ȟ2ꢇꢀꢁZKLFKꢁFOHDUO\ꢁLQGLFDWHꢁWKHꢁRFWDKHGUDOꢁ
VWHUHRFKHPLVWU\ꢁRIꢁWKHꢁFRPSOH[HVꢉ29,30 The magnetic behaviour
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1LFNHOꢆ,,ꢇꢁKDVꢁWKHꢁHOHFWURQLFꢁFRQ¿JXUDWLRQꢁꢃG8 and thus these
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The IR spectrum of 2b VKRZHGꢁDQꢁDEVRUSWLRQꢁEDQGꢁDWꢁꢃꢂꢂꢅ±
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1
absorption bands appeared at 1698 and 1584 cm-1. In the H
NMR spectra of 2b, the broad singlet at G 12.84 is assigned to
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The singlets at 8.86 and 8.82 ppm are due to the NH
OH
The UV-vis spectra of all the present cobalt(II) complexes
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The magnetic measurements on the complexes reported
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three unpaired electrons, indicating a high-spin octahedral
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and the triplet at 1.40–1.48 ppm are due to CH, OCH2 and to
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The 13C NMR spectrum of 2bꢁVKRZHGꢁVLJQDOVꢁDWꢁG 187.51,
181.85 (C=O), 96.01, 63.73, 16.25 ppm CH, OCH2 and CH3
groups (see experimental for details).
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SUHVHQWHGꢁLQꢁ6FKHPHꢁꢃꢀꢁZHUHꢁREWDLQHGꢁIURPꢁꢊꢏꢂꢁPRODUꢁUDWLRꢁ
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.
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formulae [Co(La,b,c)2(H2O)2] nH2O and [Ni(La,b,c)2(H2O)2]
Experimental
nH2O (La,b,c = ligand derived from 2a–cꢇꢉꢁ7KHꢁDQDO\WLFDOꢁGDWDꢁ
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WKHꢁFRPSOH[HVꢉꢁ7KHꢁFRORXUVꢀꢁ\LHOGVꢀꢁPHOWLQJꢁSRLQWVꢀꢁ)7,5ꢁDQGꢁ
UV-vis data of all the metal complexes are presented in Tables
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their molar conductivities (/Mꢇꢁ LQꢁ '0)ꢀꢁ ZKLFKꢁ DUHꢁ LQꢁ WKHꢁ
range 14.1–26.8 S cm2 mol-1.
Table 3 presents the most important FTIR spectral bands of
all the metal complexes. The FTIR spectra of the complexes
FDQꢁ EHꢁ FRPSDUHGꢁ ZLWKꢁ WKRVHꢁ RIꢁ WKHꢁ IUHHꢁ OLJDQGVꢁ ꢆ2a–c) to
determine the changes that might have taken place during the
complexation. The band at 1711–1696 cm–1 is characteristic
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atom in coordination.25-27
The broad IR bands of the ligands in the range 3355–
3100 cm-1ꢁPD\ꢁEHꢁGXHꢁWRꢁ2+ꢁRUꢁ1+ꢉ 25,28 The OH stretching
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3300 cm–1 and 1300, 1340 and 1368 cm-1 UHVSHFWLYHO\ꢉꢁ
The strong bands in the FTIR spectra of the free ligands,
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of the complexes. This indicates coordination through the
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the complexes, the bands observed in the 430–506 cm-1 region
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on an Electrothermal Gallenkamp apparatus and are uncorrected.
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using a Mattson 1000 FTIR spectrometer. The 1H and 13C NMR
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using TMS as an internal standard. The mass spectra (100 eV)
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F 254 Merck and Camag TLC lamp (254/366 nm). The electronic
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Unicam UV2-100 UV/VIS spectrophotometer. Molar conductances
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The atomic absorption measurements for the determination of
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atomic absorption spectrophotometer (AAS). For AAS, the cobalt
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0.5 nm; measurement 4 second.
Synthesis of the organic ligands 2a–c (LH)
General procedures for the preparation of compounds (2a–c): (a)
A solution of amine derivatives (1 mmol) in absolute chloroform
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(b) A solution of amine derivative (1 mmol) and furandione 1
ꢆꢊꢁPPROꢇꢁZDVꢁUHÀX[HGꢁLQꢁGU\ꢁEHQ]HQHꢁꢆꢊꢍꢁPOꢇꢁIRUꢁꢃꢁKꢁDQGꢁWKHꢁVROYHQWꢁ
ZDVꢁHYDSRUDWHGꢉꢁ7KHQꢁWKHꢁSUHFLSLWDWHꢁZDVꢁWUHDWHGꢁZLWKꢁGU\ꢁHWKHUꢁWRꢁ
JLYHꢁDꢁFUXGHꢁVROLGꢁWKDWꢁZDVꢁUHFU\VWDOOLVHGꢁWRꢁJLYHꢁFRPSRXQGVꢁ2a–c.
Methyl 2-[(2,4-dioxo-4-phenylbutanoyl)amino]benzoate (2a):
The compound 2aꢁ ZDVꢁ REWDLQHGꢁ DFFRUGLQJꢁ WRꢁ JHQHUDOꢁ SURFHGXUHꢁ
ꢆDꢇꢁLQꢁ\LHOGꢁꢍꢉꢊꢊꢋꢌꢁJꢁꢆꢃꢌꢉꢅꢓꢇꢀꢁDQGꢁDFFRUGLQJꢁWRꢁJHQHUDOꢁSURFHGXUHꢁ
ꢆEꢇꢁLQꢁ\LHOGꢁꢍꢉꢂꢈꢈꢋꢁJꢁꢆꢎꢅꢉꢃꢓꢇꢀꢁPꢉSꢉꢁꢊꢌꢋ±ꢊꢌꢐž&ꢁꢆꢂꢄSURSDQROꢇꢉꢁ0DVVꢁ
spectrum (100 eV) for C18H15NO5: m/e: 327.1 (3.0%), 326.0
(19.8%), 325.0(100,0%), 323.2, 294.0, 276.0, 248.0, 221.0, 180.0,
179.0, 177.9, 175.9, 152.0, 150.9, 146.9, 145.9, 129.9, 119.9, 118.9,
Ph
X
O
O
OH2
O
Y
O
NH
M
HN
Y
O
X
O
H2O
Ph
3
1
104.8, 89.9, 76.9, 68.9, 50.9. The characteristic FTIR, H NMR and
13C NMR spectra data are presented in Table 1.
Ethyl
2-[(2,4-dioxo-4-phenylbutanoyl)amino]benzoate
(2b):
M=Ni (a, b, c), Co (d, e, f); X=-COOCH3 (a, d), H (b, e),
-COOC2H5(c, f); Y=H (a, c, d, f), NO2 (b, e)
The compound 2b ZDVꢁREWDLQHGꢁDFFRUGLQJꢁWRꢁJHQHUDOꢁSURFHGXUHꢁꢆDꢇꢁ
LQꢁ\LHOGꢁꢍꢉꢊꢊꢐꢅꢁJꢁꢆꢃꢅꢉꢃꢓꢇꢀꢁDQGꢁDFFRUGLQJꢁWR general procedure (b)
LQꢁ \LHOGꢁ ꢍꢉꢂꢅꢂꢐꢁ Jꢁ ꢆꢎꢅꢉꢅꢓꢇꢀꢁ PꢉSꢉꢁ ꢊꢃꢅ±ꢊꢃꢌž&ꢁ ꢆHWKDQROꢇꢉꢁ (OHPHQWDOꢁ
Scheme 3

258 JOURNAL OF CHEMICAL RESEARCH 2008
Table 1 FTIR, 1H NMR and 13C NMR spectra of compounds 2a,b in CDCl3: (values, ppm; J (Hz))
Comp.
IR(KBr)
1H NMR
13C NMR
ĸ
ĸ
2a
3226–3220 cm-1 (C=O
OH and
12.86 (1H, bs, -OH, C=O
OH);
187.53 and 181.77 (C=O);
170.24, 162.05, 141.97, 136.83, 135.00,
135.46, 133.18, 130.84, 128.88, 125.70,
122.52, 110.34;
ĺ
ĺ
ĸ
ĸ
ĺ
NH
OH, exchangeable);
8.87 and 8.82 (1H, s, NH, NH
7.32 (1H, s, -CH);
OH);
ĺ
2994 cm-1 (CHaliph);
1698, 1584 cm-1 (C=O).
7.15–8.14 (9Harom, m);
4.00 (1H, s, CH3).
96.02 (-CH-);
54.65 (-CH3).
ĸ
ĸ
OH);
ĺ
2b
3225–3220 cm-1 (C=O
OH and
12.84 (1H, bs, -OH, C=O
ĺ
ĸ
ĸ
ĺ
NH
OH, exchangeable);
8.86 and 8.82 (1H, s, NH, NH
7.31 (1H, s, CH);
OH);
187.51 and 181.85 (C=O);
169.76, 162.02, 141.95, 136.49, 135.78,
135.45, 133.20, 130.84, 129.67, 125.66,
122.49, 118.66; 96.01 (-CH-);
63.73(-OCH2);
ĺ
2993 cm-1 (CHaliph);
1696, 1585 cm-1 (C=O).
7.14–8.14 (9Harom, m);
4.41–4.52 (2H, q, -OCH2, J = 7.1);
1.40–1.48 (3H, t, CH3, J = 7.1).
16.25 (CH3).
Table 2 Analytical and physical data for the complexes
Found (Calcd.)/%
Compd
Colour
M.p.
/°C
Yield
/%
Peff
/
M
>
B.M
@
(S cm2 mol-1)
ꢀ
Cꢀ
Hꢀ
Nꢀ
Mꢀ
ꢁ
(3a)[Ni(MEB)2(H2O)2] H2O
C36H34N2O13Ni
Light
220 Dec
82
70
63
85
69
78
2.77
56.3 (56.8) 4.5 (4.5) 3.4 (3.7) 7.8 (7.7)
52.6 (52.3) 3.6 (3.8) 7.4 (7.6) 7.9 (8.0)
56.7 (56.5) 4.75 (5.0) 3.2 (3.5) 7.3 (7.4)
21.4
25.1
14.4
20.7
26.8
11.5
Green
(760.71 g/mole
ꢁ
(3b)[Ni(HNE)2(H2O)2] H2O
32H28N4O13Ni
(734.71 g/mole)
Pale
Green
310<
3.35
2.76
C
ꢁ
(3c)[Ni(EEB)2(H2O)2] 2H2O
38H40N2O14Ni
(806.71 g/mole)
Olive
Green
190 Dec
186 Dec
310<
C
ꢁ
(3d)[Co(MEB)2(H2O)2] 0.5H2O
36H33N2O12.5Co
(751.93 g/mole)
Light
Orange
4.27 57.6 (57.45) 4.3 (4.4) 3.4 (3.7) 7.8 (7.8)
C
ꢁ
(3e) [Co(HNE)2(H2O)2] H2O
Crimson
5.06
52.8 (52.4) 4.4 (4.3) 7.4 (7.6) 8.2 (8.0)
C
32H26N4O13Co
(732.93 g/mole)
(3f) [Co(EEB)2(H2O)2]
Orange
197 Dec
4.70 59.4 (59.15) 4.7 (4.7) 3.3 (3.6) 7.1 (7.6)
C
38H36N2O12Co
(770.93 g/mole)
Table 3 Characteristic IR and Uv-vis spectra data of all the metal
Compd
OH/H2O
CHaliph.
C=OM
NH
MO
Ar–NO2
Omax (nm)
3a
3b
3c
3d
3e
3f
3421–3595 m,br
3473 w,br
2946–3057 w
2926–3073 w
2978–3061 m
2951–3063 w
2964–3061 w
2986–3061 w
1693–1598 m
1658–1600 m
1685–1598 m
1679–1595 m 3298 w
1660–1600 m 3288w
1679–1595 m 3273 w
3250 s
3285 s
3246 s
480–506 w
436–492 w
456–492 w
480–509 w
430–490 w
448–492 w
–
666, 404, 346, 308, 278
642, 428, 350, 308
644, 410, 309, 276
670, 474, 308, 274
650, 510, 382, 318, 268
640, 482, 332, 270
1479–1548 m
3435 m,br
–
–
3498 m,br
3373–3487 m,br
3481 m,br
1481–1546 m
–
Complexes: s strong, m medium, w weak, br broad.
analysis: Calc. for C19H17NO5: C, 67.25; H, 5.05; N, 4.1%. Found:
Received 20 February 2008; accepted 15 April 2008
C, 67.3; H, 5.1; N, 4.1%. The characteristic FTIR, 1H NMR and 13
NMR spectral data are presented in Table 1.
C
Paper 08/5109
doi: 10.3184/030823408X318307
N-(4-nitrophenyl)-2,4-dioxo-4-phenylbutanamide 11 (2c): The compound
2c was obtained according to general procedure (b) in yield 0.194 g
(62.2%).
References
1
S. Murai, K. Hasegawa and N. Sonoda, Angew. Chem. Int. Ed. Engl.,
1975, 14, 636.
Synthesis of the metal complexes (3a–f)
2
S.N. Shurov, I.B. Porvintsev, L.S. Kosvintseva and Yu. S. Andreichikov,
Russ. J. Org. Chem., 1997, 33, 1116. [Eng. Transl. Zh. Org. Khim., 1997,
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E. Ziegler, M. Eder, K. Belegratis and E. Prewedourakis, Monatsh. Chem.,
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N. Yu. Lisovenko, O.P. Krasnykh, Z.G. Aliev, E.S. Vostrov, O.P. Tarasova
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General procedure for the preparation of compounds 3a–f: The
appropriate quantity of the ligands 2a–c (1 mmol) was dissolved in
methanol (35 ml), and a solution of Co(AcO)2.H2O or Ni(AcO)2.4H2O
(0.5 mmol) in methanol (15 ml) was added dropwise with continuous
stirring. The mixture was stirred further for 1.5–2.5 h. at 60°C. The
SUHFLSLWDWHGꢁVROLGꢁZDVꢁWKHQꢁ¿OWHUHGꢁRIIꢀꢁZDVKHGꢁZLWKꢁFROGꢁPHWKDQROꢀꢁ
followed by diethyl ether and dried in a vacuum desiccator.
The characteristic FTIR, UV-vis, analytical and physical data of all
the metal complexes are presented in Tables 2 and 3.
3
4
5
6
7
The authors would like to thank Dr Musa Turker from the
Department of Biology, Faculty of Art and Science, Yuzuncu
Yil University, for his linguistic support.

JOURNAL OF CHEMICAL RESEARCH 2008 259
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