Template synthesis of Fe(III) and Cr(III) acyclic complexes derived from diacetyl or benzil and 1-amino-5-benzoyl-4-phenyl-1H-pyrimidine-2-one

Article abstract of DOI:10.1081/SIM-120035953

The template synthesis of diacetyl or benzil and 1-amino-5-benzoyl-4- phenyl-1H-pyrimidine-2-one in the presence of Fe(III) and Cr(III) results in the formation of acyclic complexes of the types [ML¹X₂]X, [ML²X₂

Full text of DOI:10.1081/SIM-120035953

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Template Synthesis of Fe(III) and Cr(III) Acyclic
Complexes Derived from Diacetyl or Benzil and
1‐Amino‐5‐benzoyl‐4‐phenyl‐1H‐pyrimidine‐2‐one
Mehmet Sönmez a
a Department of Chemistry, Faculty of Science and Arts , Yüzüncü Yil University , 65080,
Van, Turkey
Published online: 16 Nov 2010.
To cite this article: Mehmet Sönmez (2004) Template Synthesis of Fe(III) and Cr(III) Acyclic Complexes Derived from
Diacetyl or Benzil and 1‐Amino‐5‐benzoyl‐4‐phenyl‐1H‐pyrimidine‐2‐one, Synthesis and Reactivity in Inorganic and Metal-
Organic Chemistry, 34:4, 733-741, DOI: 10.1081/SIM-120035953
To link to this article: http://dx.doi.org/10.1081/SIM-120035953
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SYNTHESIS AND REACTIVITY IN INORGANIC AND METAL-ORGANIC CHEMISTRY
Vol. 34, No. 4, pp. 733–741, 2004
Template Synthesis of Fe(III) and Cr(III)
Acyclic Complexes Derived from Diacetyl
or Benzil and 1-Amino-5-benzoyl-
4-phenyl-1H-pyrimidine-2-one
*
¨
Mehmet Sonmez
Department of Chemistry, Faculty of Science and Arts,
Yu¨zu¨ncu¨ Yil University, Van, Turkey
ABSTRACT
The template synthesis of diacetyl or benzil and 1-amino-5-benzoyl-
4-phenyl-1H-pyrimidine-2-one in the presence of Fe(III) and Cr(III)
results in the formation of acyclic complexes of the types [ML1X2]X,
1
[ML2X2]X, and [Fe2(L1)2Cl4]Cl2 H2O, where M ¼ Fe(III), Cr(III), L
.
(benzyl derivative), or L2 (diacetyl derivative) are N2O2/ONO acyclic
ligands and X ¼ Cl, NO3). The complexes have been characterized by
elemental analyses, molar conductance, magnetic measurements, IR,
and UV/VIS spectral studies.
Key Words: Acyclic complexes; Template synthesis; Ligands; Schiff
base complexes.
*
¨
Correspondence: Mehmet Sonmez, Department of Chemistry, Faculty of Science and
Arts, Yu¨zu¨ncu¨ Yil University, 65080, Van, Turkey; E-mail: vansonmez@hotmail.com.
733
DOI: 10.1081/SIM-120035953
0094-5714 (Print); 1532-2440 (Online)
www.dekker.com
Copyright # 2004 by Marcel Dekker, Inc.

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734
INTRODUCTION
There has been considerable interest among coordination chemists in
studying the synthesis, structures, magnetic, and biological properties of acyc-
lic and macrocyclic metal complexes.[1–3] Template reactions lie at the heart
of macrocyclic or acyclic chemistry. Condensation reactions between dicarbo-
nyls and primary diamines have played an important role in the development
of synthetic acyclic and macrocyclic ligands and their metal complexes.[4,5]
Furthermore, ligands containing heterocyclic rings are known to be biologi-
cally active.[6–8] Some study groups have reported the synthesis and charac-
terization of acyclic and macrocyclic metal complexes derived from a- or
b-diketones and various diamine compounds.[4,9,10] However, acyclic com-
plexes derived from more rigid molecules such as a- or b-diketones and
N-aminopyrimidine have not been reported so far. Several Schiff base
complexes of N-amino pyrimidine-2-one have been synthesized in our
laboratory.[11,12]
In this paper, we report the preparation and characterization of mono-
nuclear and binuclear acyclic complexes with Fe(III) and Cr(III).
EXPERIMENTAL
Materials and Methods
MeOH, EtOH, BuOH, CHCl3, DMF, toluene, diethyl ether, n-heptane
benzil, and diacetyl were obtained from Fluka or Aldrich. The metal salts,
.
.
FeCl3 6H2O and Cr(NO3)3 9H2O, were obtained from E. Merck. All solvents
were dried and purified before use. 1-Amino-5-benzoyl-4-phenyl-1H pyrimi-
dine-2-one were prepared as described previously.[13]
Elemental analyses (C, H, N) were performed by using a Carlo Erba 1106
elemental analyzer. The IR spectra were obtained using KBr discs (4000–
400) cm21 on a Bio-Rad-Win-IR spectrophotometer. The electronic spectra
in the 200–900 nm range were obtained in DMF on a Unicam UV2-100
UV/Visible spectrophotometer. Magnetic measurements were carried out
by the Gouy method using Hg[Co(SCN)4] as calibrant. Molar conductances
of the acyclic Schiff base metal complexes were determined in DMF at
room temperature using a Jenway model 4070 conductivity meter.
Preparation of the Schiff Base Complexes
1-Amino-5-benzoyl-4-phenyl-1H pyrimidine-2-one (0.582 g, 2 mmol)
was dissolved in 30 mL of n-butanol, and a solution of 0.1 mL (1 mmol) of

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735
diacetyl or 0.210 g (1 mmol) benzil in 20 mL n-butanol was added drop-wise
with continuous stirring. To this was added drop-wise a solution of 1 mmol of
.
.
the metal salt [FeCl3 6H2O (0.270 g) and Cr(NO3)3 9H2O (0.400 g)] in
20 mL n-butanol with constant stirring and the mixture was boiled under reflux
for 3–6 hr. At the end of the reaction, the volume was then reduced to 10 mL
by rotary evaporation. The precipitated complexes were filtered, washed with
dry diethyl ether, followed by cold chloroform or ethanol, and dried in a
vacuum desiccator.
RESULTS AND DISCUSSION
The template condensation of 1-amino-5-benzoyl-4-phenyl-1H-pyrimi-
dine-2-one[13] and benzyl or diacetyl in the presence of FeCl3 H2O and
.
.
CrCl3 4H2O produced new tetradentate acyclic mononuclear or tridentate
.
binuclear metal complexes of the types [MLX2]X nH2O and [Fe2(L1)2Cl4]-
.
Cl2 H2O as shown in Figs. 1 and 2.
The newly synthesized Schiff base complexes are very stable at room
temperature in the solid state. The analytical data are in good agreement
with the proposed stoichiometry of the complexes. The colors, yields, melting
points, electronic, and IR absorption spectral data of all the compounds are
presented in Tables 1–3.
Infrared Spectra
Important IR bands of the acyclic complexes are given in Table 2. All
the acyclic complexes show a strong band in the region 1600–1625 cm21
Figure 1. Scheme for the preparation of the acyclic Schiff base complexes (2)–(4).

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736
Figure 2. Suggested structure of the Fe(III) complex (1) of the ligand derived from
benzil.
attributable to the coordinated (C55N) azomethine group and indicating the
condensation of the carbonyls of benzil or diacetyl and the amino groups of
1-amino-5-benzoyl-4-phenyl-1H-pyrimidine-2-one. The spectrum shows
other bands at ꢀ1660, ꢀ3060, and 1580 cm21 assigned to n(C55O), the pyr-
imidine ring, and n(Ar-C55O–M), respectively.[12,14] The nitrate complexes
exhibit intense absorption bands at ꢀ1515, ꢀ1270, and 950–1020 cm21
assigned to unidentate coordinated nitrate while free nitrate absorptions
appear[14] at 1380–1400, 810–820, and 720–730 cm21. In the chloro
complexes a band at ꢀ400 cm21 is observed which may be assigned to
the coordinated chloro group. The IR spectra of all the complexes show
absorption bands in the region 3200–3400 cm21, indicating the presence of
water molecules. The spectra of all the complexes show two absorptions in
the far-infrared region at 427–460 cm21 and 500–524 cm21, which are
assignable to n(M–N) and n(M–O), respectively.[14]
Electronic Spectra and Magnetic Measurements
The electronic spectral data for the compounds are shown in Table 3. The
spectra were recorded in DMF as solvent. In the spectrum of the N2O2 tetra-
dentate and ONO tridentate acyclic Schiff base complexes, the band of
390 nm is attributed to the azomethine group of the free ligand p ! pꢀ tran-
sition. The bands at 300–235 nm are associated with the pyrimidine ring
p ! pꢀ transition.[11,12,16] In the spectra of the complexes, the band of the
azomethine chromophore p ! pꢀ transition is shifted to about 330–
370 nm indicating that the imino nitrogen is involved in coordination to the
metal ion.
The magnetic moment values of the Cr(III) complexes are 3.90 and
3.68 B.M. which is in good agreement with the presence of three unpaired

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737

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Sonmez
738

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739
Table 3. Molar conductance, magnetic and electronic absorption spectral data of all
the compounds.
LM
(S cm2 mol21
Compounds
meff [B.M.]
)
l )
max (nm) (1, M21 cm21
(1)
3.86
54.8
712 (21), 595 (38), 504
(89), 378 (3,540)
(2)
(3)
(4)
5.86
3.90
3.68
30.6
30.1
25.6
705 (13), 594 (57), 510
(112), 365 (3,602)
595 (40), 468 (1,630), 380
(4,900)
610 (21), 478 (1,700), 370
(5,200)
electrons. The electronic spectrum of these complexes exhibits two bands at
4
4
4
4
595–610 and 468–478 nm assigned to A2g ! T2g and A2g ! T1g (F),
respectively, suggesting an octahedral environment around chromium(III).
The magnetic moment measurements of the Fe(III) complex (1) shows a mag-
netic moment of 3.86 B.M. which is abnormally small and consistent with a
dimeric structure (Fig. 2), whereas the magnetic moment for the Fe(III) com-
plex (2) is 5.86 B.M. which is monomeric and high-spin at room temperature.
The electronic spectrum of these complexes displays three bands around 714,
6
4
594, and 505 nm, which may be assigned to the transitions A1g ! T1g,
4
6
4
6A1g ! T2g, and A1g ! A1g, Eg, respectively. From the electronic and
magnetic studies, it is evident that the Fe(III) complexes possess a high-spin
octahedral configuration.[15,17]
Conductivity
Molar conductance values of 1023 M solutions (M ¼ mol dm23) of the
complexes in DMF are in the range of 25.6–54.8 V21 cm2 mol21 indicating
their slightly polar nature due to the electrolytic behavior of chlorine or
nitrate in all of the complexes.[16] The molar conductance values indicate
that complexes (2)–(4) have 1 : 1 stoichiometry whereas the [Fe2(L1)2Cl4]-
.
Cl2 H2O complex (1) is formed in 1 : 2 ratio. The complexes (2)–(4)
include one additional chloride or nitrate anion. On the other hand, the
complex (1) includes two additional chloride anions. All of these complexes
are electrolytic in nature confirming the ionic nature of the chloride or
nitrate anions.

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740
CONCLUSIONS
From the above spectral studies and elemental analyses, the following
structures (Figs. 1 and 2) have been proposed showing the mode of chelation.
The Cr(III) complexes and the Fe(III) complex (2) are of mononuclear octa-
hedral configuration while the Fe(III) complex (1) exist in a binuclear
octahedral form.
REFERENCES
1. Tenor, E.; Ludwig, R. Bioactivity of copper and zinc complexes of Schiff
bases derived from salicylaldehyde or acetylacetone. Pharmazie 1971, 26,
534–539.
ˇ
ˇ
´
2. Kotocova, K.; Sima, J. Electrochemical behaviour of a series of Fe(III)
complexes with tetradentate Schiff base ligands. Monatsh. Chem. 1994,
125, 491–495.
3. Vincent, J.B. The bioinorganic chemistry of chromium(III). Polyhedron
2001, 20, 1–26.
4. Rai, P.K.; Prasad, R.N. Cr(III), Fe(III), and Co(II) complexes of tetraaza-
macrocycles derived from 2,3-butanedione or benzyl and 1,8-diamino-
3,6-diazaoctane. Monatsh. Chem. 1994, 125, 385–394.
5. Abu Ismaiel, A.A.; Baraka, R.M.; Nasman, O.S.M. Template synthesis
and characterization of mono, and homobinucleating mixed dithiatetra-
azamacrocyclic complexes. Polyhedron 2001, 20, 455–459.
6. Hussain, M.; Al-Afaj, A.; Hossain, L. Recent studies of some pyridine,
pyrimidine and imidazole complexes. Transition Met. Chem. 1990, 13,
264–270.
7. Mishra, L.; Tiwari, L.B.; Pandey, H.N.; Upadhyay, V.; Agarwala, U.C.
Metal chelates as fungicides: Part IV. Metal(II) complexes of 4-chloro-
5,6,7,8-tetrahydrobenzothieno(2,3-d)pyrimidine. Indian J. Chem. Sect.
A 1988, 27, 742–744.
´
´
8. Salas, J.M.; Romero, M.A.; Sanchez, P.; Quiros, M. Metal complexes of
[1,2,4]-triazolo-[1,5,a]-pyrimidine derivatives. Coord. Chem. Rev. 1999,
193, 1119–1142.
9. Chen, Y.W.D.; Bard, A.J. Electrochemical and spectrophotometric
studies of iron complexes with a pentaaza macrocyclic ligand. Inorg.
Chem. 1984, 23, 2175.
10. Gerli, A.; Sabat, M.; Marzilli, L.G. Lariat-type B12 model complexes.
1. New pendant methylpyridyl costa-type organocobalt complexes pro-
vide insight into the role of the axial ligand in butterfly bending and
redox properties. J. Am. Chem. Soc. 1992, 114, 6711–6718.

ORDER
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Template Synthesis
741
¨
11. Sonmez, M.; S¸ekerci, M. Synthesis and characterization of Cu(II), Co(II),
Ni(II), and Zn(II) Schiff base complexes from 1-amino-5-benzoyl-4-
phenyl-1H-pyrimidine-2-one with salicylaldehyde. Polish J. Chem.
2002, 76, 907–914; Chem. Abstr. 2002, 137, 225,752.
¨
12. Sonmez, M. Synthesis and spectroscopic studies of Cu(II), Co(II), Ni(II),
and Zn(II) Schiff base complexes from 1-amino-5-benzoyl-4-phenyl-
1H-pyrimidine-2-one with 2-hydroxynaphthaldehyde. Polish J. Chem.
2003, 77, 397–402; Chem. Abstr. (Accession no) 2003, 292,112.
13. Akc¸amur, Y.; Altural, B.; Saripinar, E.; Kollenz, G. A simple synthesis
of functionalized 1H pyrimidines, reaction of cyclic oxalyl compound.
Monatsh. Chem. 1989, 120, 1015–1020.
14. Bellamy, L.J. The Infrared Spectra of Complex Molecules; Chapman and
Hall: London, 1978.
15. Lever, A.B.P. Inorganic Electronic Spectroscopy; Elsevier: Amsterdam,
1984.
16. Geary, W.J. The use of conductivity measurements in organic solvents
for the characterisation of coordination compounds. Coord. Chem. Rev.
1971, 7, 81.
17. Figgis, B.N.; Lewis, J. Progres in Inorganic Chemistry; Wiley Inter-
science: New York, 1964; Vol. 6.
Received April 24, 2003
Accepted January 10, 2004
Referee I: J. G. Richey
Referee II: J. E. Byrd

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