Metal complexes of ferrocenecarboxaldehyde 2,4-dichlorobenzoylhydrazone

Article abstract of DOI:10.1081/SIM-100002048

A new chelating ligand, ferrocenecarboxaldehyde 2,4-dich lorobenzoylhydrazone (HFdcbh), and seven metal complexes, M(Fdcbh)₂ [M=Co(II), Ni(II), Cu(II), Hg(II)] and Ln(HFdcbh)Cl₃. 4H₂O₂ [Ln=La(III), Sm(III) and Er(III)], have been prepared and characterized by elemental analyses, IR and ¹H NMR spectra. The deprotonated HFdcbh ligand acts as a bidentate donor, coordinating to the metal ions via its nitrogen and oxygen atoms.

Full text of DOI:10.1081/SIM-100002048

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METAL COMPLEXES OF FERROCENECARBOXALDEHYDE
2,4-DICHLOROBENZOYLHYDRAZONE
Guo-sheng Huang a , Qing-bao Song a & Yong-xiang Ma b
a Department of Chemistry , Lanzhou University , Lanzhou, 730000, P. R. China
b Department of Chemistry , Lanzhou University , Lanzhou, 730000, P. R. China
Published online: 15 Feb 2007.
To cite this article: Guo-sheng Huang , Qing-bao Song & Yong-xiang Ma (2001) METAL COMPLEXES OF
FERROCENECARBOXALDEHYDE 2,4-DICHLOROBENZOYLHYDRAZONE, Synthesis and Reactivity in Inorganic and Metal-Organic
Chemistry, 31:2, 297-302, DOI: 10.1081/SIM-100002048
To link to this article: http://dx.doi.org/10.1081/SIM-100002048
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SYNTH. REACT. INORG. MET.-ORG. CHEM., 31(2), 297–302 (2001)
METAL COMPLEXES OF
FERROCENECARBOXALDEHYDE
2,4-DICHLOROBENZOYLHYDRAZONE
Guo-sheng Huang, Qing-bao Song, and Yong-xiang Ma∗
Department of Chemistry, Lanzhou University,
Lanzhou 730000, P. R. China
ABSTRACT
A new chelating ligand, ferrocenecarboxaldehyde 2,4-dich
lorobenzoylhydrazone (HFdcbh), and seven metal complexes,
==
M(Fdcbh)2 [M Co(II), Ni(II), Cu(II), Hg(II)] and Ln(HFdcbh)Cl3.
==
4H2O2 [Ln La(III), Sm(III) and Er(III)], have been prepared and
characterized by elemental analyses, IR and 1H NMR spectra. The
deprotonated HFdcbh ligand acts as a bidentate donor, coordinating
to the metal ions via its nitrogen and oxygen atoms.
INTRODUCTION
Schiff bases from acylhydrazine and their complexes have strong antitumor
and antivirus activities (1–5) and the presence of a ferrocenyl group can improve
these properties (6). Some ferrocene derivatives are excellent nonlinear optical
materials (7) owing to their strong electron donor properties and behavior as an
electron-flow bridge. In view of their interesting structural characteristics and
wide-ranging uses, studies of the Schiff bases and their ferrocene derivatives have
∗Address correspondence to Yong-xiang Ma; E-mail:mayx@lzu.edu.cn
297
Copyright ꢀ 2001 by Marcel Dekker, Inc.
www.dekker.com
C

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298
HUANG, SONG, AND MA
O
Cl
CHO
CH NNHC
Cl
O
Cl
H2NNHC
Cl
Fe
Fe
+
Figure 1. The structure of the ligand (HFdcbp).
attracted the attention of many investigators. In the present work, we report the
synthesis and Characterization of a new ligand (HFdcbh) and its complexes with
transition metals and lanthanides. The preparation and structure of the ligand
showed as in Figure 1.
EXPERIMENTAL
Materials and Methods
Ferrocenecarboxaldehyde and 2,4-dichlorobenzoylhydrazine were prepared
by literature methods (8,9). Other reagents were analytical grade. CHN analysis
was carried out with an Elementary Vario EL elemental analyzer. The IR spec-
tra were recorded on a Nicolet 170 SX spectrophotometer as KBr discs in the
1
4000–200 cm−1 region H NMR spectra were measured with a FT-80A NMR
spectrometer using DMSO-d6 or CDCl3 as solvent and TMS as internal stan-
dard. Molar conductances were recorded by a DDS-IIA conductometer in DMF
at 15◦C. Melting points were determined on a RY-1 melting point apparatus and
are uncorrected.
Preparation of HFdcbh
Ferrocenecarboxaldehyde (2.14 g, 10 mmol) was dissolved in 15 mL of
anhydrous ethanol, which was added dropwise into a solution of 2,4-dichloro-
benzoylhydrazine (2.05 g, 10 mmol) in anhydrous ethanol (60 mL) under stirring
and refluxing. A red precipitate appeared immediately and the mixture was refluxed
for 2 h with stirring. The mixture was cooled to room temperature, and the product
was collected on a Bu¨chner funnel, washed twice with ethanol and diethyl ether,
respectively, recrystallized in anhydrous ethanol, and dried in vacuo. Reddish
orange crystals were obtained. Yield 4.0 g (90%), m.p. 230◦C (dec.).

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METAL COMPLEXES OF A NEW CHELATING LIGAND
299

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HUANG, SONG, AND MA
Preparation of Co, Ni, Cu, and Hg Complexes
M(OAc)2.nH2O (0.25 mmol) was dissolved in 25 mL of anhydrous ethanol
with heating (50◦C), and this solution was added dropwise into a solution of
HFdcbh (0.2 g, 0.50 mmol) in 50 mL anhydrous ethanol with stirring at room
temperature. Then the mixture was stirred continuously for 20 min at room tem-
perature and for 6–8 h under reflux. A red solid was formed which was collected
immediately on a Bu¨chner funnel, washed twice with warm ethanol and diethyl
ether, respectively, and dried in vacuo. The yield and elemental analysis results of
the complexes are listed in Table I.
Preparation of Lanthanide Complexes
A solution of HFdcbh (0.4 g, 1.0 mmol) in 50 mL of anhydrous ethanol
was added dropwise into a solution of LnCI3 (0.5 mmol) (Ln = La, Sm and Er)
in 60–70 mL of anhydrous ethanol with heating and stirring. The mixture was
stirred for 12 h under reflux. Then it was concentrated under reduced pressure in a
warm water bath until its volume was reduced to 1/3, cooled, filtered and the solid
washed with warm ethanol and diethyl ether, and dried in vacuo. The yields and
analytical data of the complexes are shown in Table I.
RESULTS AND DISCUSSION
HFdcbh and its complexes are colored solids that remain stable in air be-
low 200◦C. Their physical properties are shown in Table I. The elemental anal-
yses results show that the ligand coordinates to the central metal ions in two
Table II. Some Characteristic IR Wave Numbers of the Ligand and Its Complexes a
(cm−1
)
–
==
== – ==
==
== –
ν(N C O)
–
–
Compd. ν(N H) ν(C 0) ν(C N H C) ν(C N)
ν(C O) ν(N N)
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
3238 s 1662 vs
—
1622 m
1619 m
1619 m
1629 m
–
1604 s
–
–
999 w
–
–
–
–
–
–
–
–
1580 s 1523 s, 1352 s 1245 w 1007 m
1587 s 1534 vs, 1352 vs 1241 w 1011 m
1584 s 1510 vs, 1358 vs 1241 w 1012 m
1587 s 1510 s, 1369 vs 1248 w 1001 m
1587 s
1585 s
1588 vs
3236 sh 1656 vs
3230 sh 1650 vs
3235 sh 1654 vs
–
–
–
–
–
–
1000 m
1002 m
1001 m
–
–
ash = shoulder, s = strong, vs = very strong, m = medium, w = weak.

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METAL COMPLEXES OF A NEW CHELATING LIGAND
301
Table III. 1H NMR Data (δ) b of the Ligand and Its Complexes (5) and (6)
–
N H
==
N CH
–
C6H3Cl2
No.
C5H4
C5H5
(1) 11.68 (s, 1H) 8.10 (s, 1H) 7.48–7.88 (m, 3H) 4.68 (d, 2H), 4.48 (d, 2H) 4.23 (s, 5H)
(5) 7.78 (s, 2H) 7.30–7.70 (m, 6H) 4.76 (d, 4H), 4.46 (d, 4H) 4.34 (s, 10H)
–
(6) 11.71 (br, 1H) 7.75 (s, 1H) 7.45–7.66 (m, 3H) 4.65 (d, 2H), 4.46 (d, 2H) 4.24 (s, 5H)
b
br = broad, s = singlet, d = doublet, m = multplet.
forms, i.e. M[Fdcbh]2 and Ln[HFdcbh]Cl3 · 4H2O. The molar conductivity data
approach the reported values of a non-electrolyte for transition metal complex
(2.1–8.0 ꢁ−1cm2 · mol−1) or 1:1 electrolyte for the lanthanide complexes (81–
96 ꢁ−1cm2 · mol−1) in the literature (10).
IR Spectra
The main features of the IR spectra of free HFdcbh and its complexes are
shown in Table II. The bands appearing at 3228, 1662, 1604 and 999 cm−1 are
–
==
==
–
attributed to ν(N H), ν(C O), ν(C N) and ν(N N). The IR spectra of the com-
plexes (2)–(5) show apparent changes as compared with that of the ligand. The
–
==
bands attributed to ν(N H) and ν(C O) had disappeared, while four new bands
appeared at about 1620, 1520, 1355 and 1245 cm−1 arising from ν(C N N C),
== – ==
–
ν(NCO) and ν(C O). The IR spectra of the complexes (6)–(8) exhibited few
==
==
changes, and only the bands due to ν(C O) and ν(C N) are shifted to lower
frequency by 6–12 or 16–19 cm−1, respectively. These results indicate that the
ligand coordinates to central metal ions either in the deprotonated enol form (for
transition metals) or in the neutral keto-form (for the lanthanides).
1H NMR Spectra
The 1H NMR data for (1) and its complexes (5) and (6) are listed in Table III.
The proton signals at 11.68, 8.10, 7.48–7.88, 4.68 and 4.48, and 4.23 ppm for (1)
==
arise from NH, N CH, aryl ring, substituted and unsubstituted cyclopentadienyl,
respectively. The proton signal due to NH disappeared for (5) and remained un-
==
changed for (6). The proton signal due to N CH for (5) and (6) shifted upfield
by 0.3 and 0.2 ppm, respectively. These results agree with those obtained from
elemental analyses and IR spectra.
Summarizing the present results, we consider that the ligand HFdcbh forms
two types of complex. When using metal acetate, the ligand coordinates to the

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HUANG, SONG, AND MA
Figure 2. Proposed structure of the complexes of HFdcbh.
central ions as deprotonated enol-form (A) (11) and using metal chloride it coor-
dinates as neutral keto-form (B) (12) as shown in Figure 2.
REFERENCES
1. Ali and, M. A. and Livingstone, S. E.; Coord. Chem. Rev., 1974, 13, 101.
2. Cleare, M. J.; Coord. Chem. Rev., 1974, 12, 349.
3. Williams, D. R.; Chem. Rev., 1972, 72, 203.
4. Das, M. and Livingstone, S. E.; Inorg. Chim. Acta, 1976, 19, 5.
5. Ali, M. A. and Bose, R. N.; Polyhedron, 1984, 3, 517.
6. Ali, M. A; Livingstone, S. E. and Phillips, D. J.; Inorg. Chim. Acta, 1973,
7, 79.
7. Long, N. J.; Angew. Chem. Int. Ed. Engl., 1995, 34, 21.
8. Graham, P. J., Lindsey, R. V.; Parshall, G. W.; Peterson, M. L. and Whitman,
G. M. J. Am. Chem. Soc., 1957, 79, 3416.
9. Singh, B. and Srivastava, P.; Trans. Met. Chem., 1986, 11, 106.
10. Geary, W. J.; Coord. Chem. Rev., 1971, 71, 81.
11. Ma, Y. X.; Li, F.; Sun, H. S. and Xie, J. S.; Inorg. Chim. Acta, 1988, 149,
209.
12. Ma, Y. X. and G. Zhao; Polyhedron, 1988, 7(12), 1101–1105.
Received August 17, 2000
Accepted November 29, 2000
Referee I: J. P. Jasinski
Referee II: E. Rosenberg

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