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Departamento de Qumica, Universidade Federal de Sao Carlos, Rodavia Washington Luiz, Km 235, Caixa Postal 676,
13565-905 Sao Carlos, Sao Paulo, Brazil
Received 22 June 2006; accepted 9 November 2006
Abstract
Eight chromium(III) complexes of tetradentate Schi bases have been prepared in situ by condensing of a substituted salicylaldehyde
compound with ethylenediamine. These were characterized by elemental analysis, m.p., IR, molar conductivity, magnetic moment measurements, and electronic spectra. The free ligands were also characterized by 1H and 13C NMR spectra. The 13C NMR spectra are discussed in terms of possible substituent eects. The IR and electronic spectra of the free ligand and the complexes are compared and
discussed. The electrospray ionization (ESI) mass spectra of four free ligands and their complexes were measured. The deconvolution
of the visible spectra of the complexes, C2v symmetry, in DMSO yields three peaks at ca. 15 60017 600, 18 40020 400 and 20 000
23 100, and are assigned to the three dd transitions, 4B1g ! 4Eg(4T2g); 4B1g ! 4B2g(4T2g); 4B1g ! 4Eg(4T1g), respectively. The complexes
showed magnetic moment in the range of 3.54.2 BM which corresponds to three unpaired electrons.
2006 Elsevier Ltd. All rights reserved.
Keywords: Chromium(III) complexes; Schi bases; Salen; Electronic spectra; Deconvolution; Substituent eects
1. Introduction
The chemistry of Schi bases is an area of increasing
interest. Metal complexes with these bases have numerous
applications, such as, in the treatment of cancer [1], as
antibactericide agents [2,3], as antivirus agents [46], as
fungicide agents [7,8] and for other biological properties
[911]. Several applications have been related for these
complexes in chemical analysis [12], absorption and transport of oxygen [13], in pesticides [14] and heterogeneous
and homogeneous catalysis for oxidation and polymerization of organic compounds [1518].
Chromium with +3 oxidation state, under physiological
conditions, is neither an oxidizing nor a reducing agent,
however, chromium(III) due its d3 electronic conguration
forms stable and substationally inert metal complexes [19].
Complexes of chromium(III) are much less cytotoxic than
*
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in ethanol (50 ml) was added dropwise an ethanolic solution (10 ml) of 2.0 mmol ethylenediamine. This mixture
was then heated for 2 h. Afterwards the mixture was cooled
to room temperature, then cooled for 24 h at 5 C. The
solid was ltered and washed with cold ethanol (5 ml at
5 C) and dried over silica. The ligands were used without
further purication.
13
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adjusted coecient of determination of the Jandel Scientic Software PeakFit program [42] was also used in
the determination of the goodness of t [43].
3. Results and discussion
The complexes of chromium(III) are stable in air, both
in solution and in the crystalline state. The solids are various shades of brown. The yields of the puried complexes
varied from 13.7% to 53.7%. The variation is due to dierences in the solubility of the starting ligands and the nal
complexes. The complexes showed magnetic moment in
the range of 3.54.2 BM which corresponds to three
unpaired electrons [44].
The molar conductance of the complexes was an aid for
proposing their formulas. For pure DMSO the measured conductivity was 15.1 S cm2 mol1, for a 1:1 electrolyte, KCl,
1.00 103 mol L1 in DMSO, the molar conductivity was
46.0 S cm2 mol1 and 126.5 S cm2 mol1 for the 2:1 electrolyte, MgCl2, 1.00 103 mol L1 in DMSO. The molar conductances in DMSO solutions, at 25 C, with a concentration
of 1 103 mol L1, are: [Cr(L5)(H2O)2]Cl, 54 S cm2 mol1;
[Cr(L6)(H2O)2]Cl, 39 S cm2 mol1; [Cr(L7)(H2O)2]Cl, 45 S
cm2 mol1 and [Cr(L8)(H2O)2]Cl, 50 S cm2 mol1. These
data are, as expected, for a 1:1 electrolyte. The complexes,
[Cr(L1)(OH)(H2O)], 14 S cm2 mol1; [Cr(L2)(OH)(H2O)],
13 S cm2 mol1; [Cr(L3)(OH)(H2O)], 26 S cm2 mol1 and
[Cr(L4)(OH)(H2O)], 18 S cm2 mol1, are neutral electrolytes.
Solutions of the complexes were also tested with AgNO3 for
free chloride on with the results conrming the proposed
structures. The proposed structural representations of the
complexes and their abbreviations are given in Fig. 2.
The results of the microanalyses, the molar conductance
and tests with AgNO3 indicate that two series of complexes
are formed by the same synthetic procedure [41]. The rst
series of complexes [Cr(Ln)(H2O)2]Cl, is the expected product of the synthesis. The second series, [Cr(Lm)(OH)(H2O)],
is related to the rst series by the deprotonation of a coordinated water forming a neutral complex. A slow addition
rate results in the expected [Cr(Ln)(H2O)2]Cl product.
However, either if the potassium carbonate is added too
fast or if amount is larger than the value calculated, the
product is [Cr(Ln)(OH)(H2O)]. The potassium carbonate
is used in the synthesis to deprotonate the Schi base H2Ln.
3.1. IR spectra
The IR spectra of the free ligands and the complexes
exhibit various bands in the 2504000 cm1 region. A typical spectrum of the free ligand and the corresponding chromium(III) are shown in Fig. 3. The OH stretching
frequency of the ligand is expected in the 33003800 cm1
region, however, this frequency is generally displaced to
the 28402960 cm1 region due to the internal hydrogen
bridge OH N@C [45,46]. As the hydrogen bond becomes
stronger, the bandwidth increases, and this band sometimes
is not detected. Hydrogen bonds in these Schi bases are
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R2
R2
R2
Cl-
Cr
Cr
O
R1
OH2
OH
R2
R1
OH2
R
H
R
H
L
OH
Complexes
[Cr(L1)(OH)(H2O)]
Br
OH
[Cr(L2)(OH)(H2O)]
3
R1
1
R
H
O
R1
OH2
2
R
NO 2
L
H2O
Complexes
[Cr(L5)(H2O)2]Cl
Br
Br
H2O
[Cr(L6)(H2O)2]Cl
Cl
OH
[Cr(L )(OH)(H2O)]
Cl
Cl
H2O
[Cr(L7)(H2O)2]Cl
MeO
OH
[Cr(L4)(OH)(H2O)]
H2O
[Cr(L8)(H2O)2]Cl
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Table 1
1
H NMR data of free ligands with tetramethylsilane, TMS, as internal standard (chemical shifts in ppm and J in Hz)
dOH
dN@C(H)
dPh
C4 H
C6 H
C5 H
C3 H
d@NCH2
dOH
dN@C(H)
dPh
C4 H
C3 H
C6 H
d@NCH2
dOCH3
dOH
dN@C(H)
dPh
C4 H
C6 H
C3 H
d@NCH2
H2L1a
H2L2a
>12.00
8.57 (s, 2H)
>12.00
8.56 (s, 2H)
7.41
7.30
6.86
6.84
3.90
a
b
c
H2L3c
H2L4c
7.51
7.23
6.90
3.97
7.26
6.85
6.74
3.95
3.75
H2L5a
H2L6a
>12.00
8.75 (s, 2H)
>12.00
8.56 (s, 2H)
8.42
8.07
7.73
4.00
H2L
dOH
dN@C(H)
dPh
C4 H
C6 H
dNCH2
>12.00
8.46 (s, 2H)
DMSO-d6.
s = singlet, d = doublet, dd = doublet of doublets, ddd = doublet of doublet of doublets.
CDCl3.
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Table 2
13
C NMR data of free ligands with tetramethylsilane, TMS, as internal standard (chemical shifts in ppm)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(OCH3)
a
b
H2L1a
H2L2b
H2L3a
H2L4a
H2L5b
H2L6b
H2L7a
H2L8b
118.6
161.0
116.9
132.3
118.7
131.4
166.6
59.7
119.5
160.5
120.7
135.3
109.4
133.9
166.1
58.8
119.3
159.5
118.6
132.3
123.3
130.5
165.3
59.6
118.2
155.0
117.5
119.4
151.9
114.8
166.2
59.7
55.8
122.0
167.2
121.2
130.7
135.6
128.9
166.2
54.2
118.7
162.1
114.1
138.5
106.5
134.4
166.8
55.3
118.3
159.5
119.4
132.3
130.5
123.4
165.2
59.6
118.6
164.8
92.6
149.0
110.1
141.3
166.7
56.4
CDCl3.
DMSO-d6.
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groups on the aromatic ring generally result in a bathochromic shift in all observed bands. The p ! p*-type
transition due to the C@N chromophore shifts to lower
energies on complexation. In general, the p ! p*-type
transition due to the aromatic ring undergoes a similar
smaller shift.
Another dierence observed in the electronic spectra of
the chromium(III) complexes, compared to the spectra of
the corresponding free ligand, is associated with the
appearance of a broad low intensity band at ca. 500 nm.
This band is attributed to the dd transitions of the chromium ion. These bands are of low molar absorptivity, e,
being Laporte forbidden transitions. Another important
characteristic is the absence of the n ! p* band. The formation of the metalnitrogen bond stabilizes the electron
pair on the nitrogen atom [64]. The appearance of a strong
band between 390 and 430 nm is attributed to ligand-tometal charge-transfer bands. These charge-transfer transitions probably occur form the p-orbitals of the Schi bases
to the d-orbitals of chromium.
The Gaussian/Lorentzian analysis of the visible portion,
11 76025 000 cm1 of the optical absorption spectrum
yields three peaks, due to a symmetry that is less than octahedral in a six-coordinate complex. Each of the triply
degenerate T terms is split into two new terms, an E and
an A or B, with the result that six transitions are now
expected instead of three [66,67]. For the chromium(III)
complexes with C2v symmetry six transitions I: 4B1g !
4
Eg(4T2g); II: 4B1g ! 4B2g(4T2g); III: 4B1g ! 4Eg(4T1g); IV:
4
B1g ! 4A2g(4T1g); V: 4B1g ! 4A2g(4T1g(P)); VI: 4B1g
! 4Eg(4T1g(P)) were proposed. The three transitions
appear at higher energies and are covered by ligand-tometal charge-transfer bands. Thus, only the three rst transitions are calculated as shown in Fig. 6. The calculated
values for the absorption maximum, the molar absorptivity, and the oscillator strength [68] for each peak are given
in Table 3.
Complexes
Banda
[Cr(L1)(OH)(H2O)]
[Cr(L2)(OH)(H2O)]
[Cr(L3)(OH)(H2O)]
[Cr(L4)(OH)(H2O)]
[Cr(L5)(H2O)2]Cl
[Cr(L6)(H2O)2]Cl
[Cr(L7)(H2O)2]Cl
[Cr(L8)(H2O)2]Cl
a
b
kmax 103
(cm1)
emax (dm3
mol1 cm1)
Oscillator
strengthb
(R = 0.13%)c
I
II
III
16.14
20.39
23.11
61.5
281.6
374.6
9.27 104
3.99 103
1.62 103
(R = 0.10%)
I
II
III
15.67
19.45
22.78
75.9
143.6
147.9
1.39 103
2.88 103
3.32 103
(R = 0.05%)
I
II
III
15.85
20.11
22.43
53.0
188.9
282.6
9.27 104
3.99 103
1.62 103
(R = 0.07%)
I
II
III
15.59
19.06
21.52
91.1
205.1
294.2
1.47 103
3.75 103
2.95 103
(R = 0.66%)
I
II
III
16.20
18.35
19.95
75.9
117.7
629.3
1.05 103
1.46 103
8.54 103
(R = 0.65%)
I
II
III
17.62
19.37
21.29
44.7
179.5
240.6
1.01 103
2.10 103
2.63 103
(R = 0.35%)
I
II
III
16.54
18.46
21.58
24.1
116.7
239.9
1.98 104
1.74 103
4.30 103
(R = 0.15%)
I
II
III
16.46
19.79
22.52
64.7
194.0
204.3
1.25 103
3.57 103
5.27 103
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