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Polyhedron xxx (2006) xxxxxx

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Synthesis, characterization, and spectroscopic studies

of tetradentate Schi base chromium(III) complexes
Pedro E. Aranha, Mirian P. dos Santos, Sandra Romera, Edward R. Dockal

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
*

Corresponding author. Tel.: +55 16 3351 8095.

E-mail address: dockal@dq.ufscar.br (E.R. Dockal).

chromium(VI) to cultured human cells [20]. Chromium(III)

is an essential nutrient that is involved in the glucose tolerance factor (GTF) in maintenance of normal carbohydrate
and lipid metabolism [21,22]. Insucient dietary intake
of chromium is linked to increase risk factors associated
with Type II diabetes and cardiovascular diseases. Schi
base complexes of chromium(III) such as N,N 0 -ethylene
bis(salicylidene-iminate)diaquochromium(III)chloride, [Cr(salen)(H2O)2]Cl used as a new model of GTF, was also
shown to reduce the symptoms of diabetes like, hyperglycemia and cholesterol in diabetic rats [23,24].
Chromiumsalen complexes are well-known catalysts,
both in heterogeneous and homogeneous systems. Other
applications of theses complexes are reported, such as,
the stereoselective alkene epoxidations [2528], alcohol
oxidations [29], the asymmetric addition of organometallic
reagents to aldehydes [30,31] and asymmetric hetero
DielsAlder reactions [32,33]. Recently, the interaction
of DNA with complexes [Cr(Schi base)(OH2)2]ClO4
[34,35], was reported. These complexes have been shown

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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.

Fig. 1. Ligands used in this study and the

13

C NMR numbering system.

to bring about apoptosis in lymphocyte cell cultures [36].

The (salen)chromium(III)/DMAP catalyst system is used
in the xation of CO2 with epoxides to form carbonates
[37].
As part of the ongoing investigations [38] by our group
of metalsalen catalyzed oxidations and of insulin-mimetic
complexes [39] we prepared complexes of chromium
salen. In this paper we describe chromium(III) complexes
of the tetradentate Schi bases, N,N 0 -bis(salicylidene)
ethylene-diamine, H2L1; N,N 0 -bis(5-bromosalicylidene)
ethylenediamine, H2L2; N,N 0 -bis(5-chlorosalicylidene)ethylenediamine, H2L3; N,N 0 -bis(5-methoxysalicylidene)ethylenediamine, H2L4; N,N0 -bis(5-nitrosalicylidene)ethylenediamine,
H2L5;
N,N 0 -bis(3,5-diclorosalicylidene)ethylenediamine,
6
H2L ; N,N 0 -bis(3,5-dibromo-salicylidene)ethylenediamine,
H2L7; and N,N 0 -bis(3,5-diiodosalicylidene)ethylenediamine, H2L8. A structural representation of the ligands,
their abbreviations, and numbering system of the carbons
for 13C NMR are given in Fig. 1.
2. Experimental
2.1. Reagents
Ethylenediamine, 99%; salicylaldehyde, 98%; 5-bromosalicylaldehyde, 98%; 5-chlorosalicylaldehyde, 98%; 5methoxyosalicylaldehyde, 98%; 5-nitrosalicylaldehyde,
99%; 3,5-dibromosalicylaldehyde, 98%; 3,5-dichlorosalicylaldehyde, 99%; 3,5-diiodosalicylaldehyde, 97%; (methyl
sulfoxide)-d6, 99.9 atom% D, DMSO-d6; chloroform-d
99.8 atom% D, CDCl3 (Aldrich Chemical Co.) and
CrCl3 6H2O (Riedel-de-Haen Inc.) were used as received.
All other solvents and reagents were obtained commercially and were used without further purication.
2.2. Preparation of the Schi bases
The Schi bases were prepared in a similar manner [40]
by the following procedure: to a stirred solution of
4.0 mmol of the appropriate substituted salicylaldehyde

2.2.1. Ligand H2L1

Brilliant yellow akes. Yield: 0.498 g, 92.8%. m.p.: 125
126 C (uncorrected). Anal. Calc. for C16H16N2O2: C, 71.6;
H, 6.0; N, 10.4. Found: C, 71.7; H, 6.0; N, 10.4%. Selected
IR bands (KBr, cm1): 1634s, mC@N; 1576m, mC@C; 1371m,
mCN; 1283m, mCO. UVVis spectrum in DMSO [kmax (nm),
e (M1 cm1)]: 317 (8420), 402 (465). Mass spectrum, ESI/
MS in DMSO [m/z(%)]: 267(18), 245(19), 227(51), 172(73),
157(39), 141(100).
2.2.2. Ligand H2L2
Light yellow crystals. Yield: 0.794 g, 93.2%. m.p.: 171
173 C (uncorrected). Anal. Calc. for C16H14N2O2Br2: C,
45.1; H, 3.3; N, 6.6. Found: C, 45.5; H, 3.3; N, 6.7%.
Selected IR bands (KBr, cm1): 1632s, mC@N; 1565m, mC@C;
1360m, mCN; 1274s, mCO; 1072m, mCBr. UVVis spectrum
in DMSO [kmax (nm), e (dm3 cm1 mol1)]: 329 (7050), 421
(735). Mass spectrum, ESI/MS, in DMSO [m/z(%)]:
425(43), 385(6), 339(25), 325(37), 249(46), 201(100).
2.2.3. Ligand H2L3
Light yellow crystals. Yield: 0.560 g, 83.0%. m.p.: 155
157 C (uncorrected). Anal. Calc. for C16H14N2O2Cl2: C,
57.0; H, 4.2; N, 8.3. Found: C, 57.0; H, 4.2; N, 8.4%.
Selected IR bands (KBr, cm1): 1633s, mC@N; 1570m, mC@C;
1362m, mCN; 1275m, mCO; 1092m mCCl. UVVis spectrum
in DMSO [kmax (nm), e (dm3 cm1 mol1)]: 328 (7510), 423
(670). Mass spectrum, ESI/MS, in DMSO [m/z(%)]: 338(4),
254(36), 215(30), 179(100).
2.2.4. Ligand H2L4
Yellow powder. Yield: 0.560 g, 85.4%. m.p.: 150152 C
(uncorrected). Anal. Calc. for C18H20N2O4: C, 65.8; H, 6.1;
N, 8.5. Found: C, 66.1; H, 6.0; N, 8.4%. Selected IR bands
(KBr, cm1): 1638s, mC@N; 1587m, mC@C; 1357m, mCN;
1274m, mCO; 1228m, mCOC. UVVis spectrum in DMSO
[kmax (nm), e (dm3 cm1 mol1)]: 346 (8630), 430 (140).
2.2.5. Ligand H2L5
Yellow powder. Yield: 0.580 g, 81.0%. m.p.: 261263 C
(uncorrected). Anal. Calc. for C16H14N4O6: C, 53.6; H, 3.9;
N, 15.6. Found: C, 53.3; H, 3.8; N, 15.8%. Selected IR
bands (KBr, cm1): 1646s, mC@N; 1614s, mC@C; 1542m,
mNO2 ; 1353m, mCN; 1324s mNO2 . UVVis spectrum in DMSO
[kmax (nm), e (dm3 cm1 mol1)]: 365 (15 100), 420 (17 400).
Mass spectrum, ESI/MS, in DMSO [m/z(%)]: 359(11),
259(6), 228(10), 179(58), 157(100).

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2.2.6. Ligand H2L6

Yellow powder. Yield: 1.036 g, 88.7%. m.p.: 238241 C
(uncorrected). Anal. Calc. for C16H12N2O2Br4: C, 32.9; H,
2.1; N, 4.8. Found: C, 33.1; H, 2.2; N, 4.9%. Selected IR bands
(KBr, cm1): 1636s, mC@N; 1592m, mC@C; 1356w, mCN; 1287w,
mCO. UVVis spectrum in DMSO [kmax (nm), e
(dm3 cm1 mol1)]: 289 (6180), 335 (4340), 431 (6340).

5.5. Found: C, 37.8; H, 2.6; N, 5.3%. Selected IR bands

(KBr, cm1): 1627s, mC@N; 1592m, mC@C; 1377m, mCN;
1300m, mCO; 582w, mCrO; 378w, mCrN. UVVis spectrum
in DMSO [kmax (nm), e (dm3 cm1 mol1)]: 284 (12 400),
341 (1294), 407 (980). Mass spectrum, ESI/MS, in DMSO
[m/z(%)]: 633(10), 521(16), 470(9), 339(52), 325(54),
311(42), 283(51), 249(100). le(298 K): 4.13 BM.

2.2.7. Ligand H2L7

Yellow powder. Yield: 0.696 g, 85.7%. m.p.: 208210 C
(uncorrected). Anal. Calc. for C16H12N2O2Cl4: C, 47.3; H,
3.0; N, 6.9. Found: C, 47.0; H, 2.7; N, 6.7%. Selected IR
bands (KBr, cm1): 1639s, mC@N; 1552w, mC@C; 1369w,
mCN; 1289w, mCO. UVVis spectrum in DMSO [kmax
(nm), e (dm3 cm1 mol1)]: 286 (5600), 334 (4570), 431
(5610).

2.3.3. Preparation of [Cr(L3)(OH)(H2O)]

Brown powder. Yield 0.372 g, 44.0%. m.p.: >360 C.
Anal. Calc. for C16H15N2O4Cl2Cr: C, 45.5; H, 3.6; N, 6.6.
Found: C, 45.1; H, 3.2; N, 6.4%. Selected IR bands
(KBr, cm1): 1629s, mC@N; 1599m, mC@C; 1379m, mCN;
1302m, mCO; 584w, mCrO; 376w, mCrN. UVVis spectrum
in DMSO [kmax (nm), e (dm3 cm1 mol1)]: 344 (2000),
413 (1570). Mass spectrum, ESI/MS, in DMSO [m/z(%)]:
543(8), 319(10), 257(10), 215(10), 184(27), 179(100),
153(63), 145(19). le(298 K): 3.92 BM.

2.2.8. Ligand H2L8

Yellow powder. Yield: 0.854 g, 55.0%. m.p.: 240242 C
(uncorrected). Anal. Calc. for C16H12N2O2I4: C, 24.9; H,
1.6; N, 3.6. Found: C, 24.6; H, 1.6; N, 3.3%. Selected IR
bands (KBr, cm1): 1630s, mC@N; 1580m, mC@C; 1353m,
mCN; 1281m, mCO. UVVis spectrum in DMSO [kmax
(nm), e (dm3 cm1 mol1)]: 296 (5800), 344 (5000), 438
(6520).
2.3. Preparation of the chromium(III) complexes
The chromium(III) complexes were prepared essentially
as described [41]. The following procedure was used: ethylenediamine (0.12 g, 2.0 mmol) and the appropriate salicylaldehyde (4.0 mmol) were added to a solution of
chromium(III) chloride hexahydrate (0.53 g, 2.0 mmol) in
ethylene glycolwatermethanol (1:1:3, 50 ml). After the
mixture was reuxed for 30 min, potassium carbonate
(0.21 g, 1.5 mmol) was gradually added to the solution,
then reuxing the solution for about 34 h. The precipitate
was ltered, washed with cold water (5 ml) and cold ethanol (5 ml) and dried over silica. The complex was recrystallized from 95% ethanol and dried over silica in a desiccator
at room temperature.
2.3.1. Preparation of [Cr(L1)(OH)(H2O)]
Brown powder. Yield: 0.253 g, 35.8%. m.p.: 245250 C
decomposition (uncorrected). Anal. Calc. for C16H17
N2O4Cr: C, 54.4; H, 4.9; N, 7.9. Found: C, 54.7; H, 5.2;
N, 7.95%. Selected IR bands (KBr, cm1): 1638s, mC@N;
1540m, mC@C; 1372m, mCN; 1295m, mCO; 538w, mCrO;
375w, mCrN. UVVis spectrum in DMSO [kmax (nm), e
(dm3 cm1 mol1)]: 277 (14 000), 334 (3420), 393 (3700).
Mass spectrum, ESI/MS, in DMSO [m/z(%)]: 474(60),
428(17), 319(20), 241(22), 215(20), 179(100), 153(88).
le(298 K): 3.92 BM.
2.3.2. Preparation of [Cr(L2)(OH)(H2O)]
Brown powder. Yield: 0.358 g, 35.0%. m.p.: >360 C.
Anal. Calc. for C16H15N2O4Br2Cr: C, 37.6; H, 2.95; N,

2.3.4. Preparation of [Cr(L4)(OH)(H2O)]

Brown powder. Yield: 0.445 g, 53.8%. m.p.: >360 C.
Anal. Calc. for C18H21N2O6Cr: C, 52.3; H, 4.8; N, 6.8.
Found: C, 52.2; H, 5.1; N, 6.6%. Selected IR bands
(KBr, cm1): 1628s, mC@N; 1563m, mC@C; 1388m, mCN;
1305m, mCO;. 5 69w, mCrO; 380w, mCrN. UVVis spectrum
in DMSO [kmax (nm), e (dm3 cm1 mol1)]: 357 (2010), 430
(1380). le(298 K): 4.00 BM.
2.3.5. Preparation of [Cr(L5)(H2O)2]Cl
Brown powder. Yield: 0.409 g, 46.0%. m.p.: >360 C.
Anal. Calc. for C16H16N4O8ClCr: C, 40.1; H, 3.4; N,
11.7. Found: C, 40.6; H, 3.3; N, 12.0%. Selected IR bands
(KBr, cm1): 1638s, mC@N; 1580m, mC@C; 1390m, mCN;
1304m, mCO; 569w, mCrO; 375w, mCrN. UVVis spectrum
in DMSO [kmax (nm), e (dm3 cm1 mol1)]: 375 (19 200).
Mass spectrum, ESI/MS, in DMSO solutions [m/z(%)]:
564(12), 476(13), 359(32), 305(56), 275(52), 259(68),
227(100), 215(21). le(298 K): 3.51 BM.
2.3.6. Preparation of [Cr(L6)(H2O)2]Cl
Brown powder. Yield: 0.363 g, 25.7%. m.p.: >360 C.
Anal. Calc. for C16H14N2O4ClBr4Cr: C, 27.2; H, 2.0; N,
4.0. Found: C, 27.5; H, 1.8; N, 3.7%. Selected IR bands
(KBr, cm1): 1634s, mC@N; 1578m, mC@C; 1358w, mCN;
1298w, mCO; 575w, mCrO; 370w, mCrN. UVVis spectrum
in DMSO [kmax (nm), e (dm3 cm1 mol1)]: 286 (16 400),
336 (4570), 410 (4180). le(298 K): 4.19 BM.
2.3.7. Preparation of [Cr(L7)(H2O)2]Cl
Brown powder. Yield: 0.522 g, 53.0%. m.p.: >360 C.
Anal. Calc. for C16H14N2O4Cl5Cr: C, 36.4; H, 2.7; N, 5.3.
Found: C, 36.2; H, 2.7; N, 5.5%. Selected IR bands
(KBr, cm1): 1628s, mC@N; 1519w, mC@C; 1376w, mCN;
1290w, mCO; 580w, mCrO; 357w, mCrN. UVVis spectrum
in DMSO [kmax (nm), e (dm3 cm1 mol1)]: 319 (4060),
415 (2370). le(298 K): 4.05 BM.

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2.3.8. Preparation of [Cr(L8)(H2O)2]Cl H2O

Brown powder. Yield: 0.245 g, 13.4%. m.p.: >360 C.
Anal. Calc. for C16H164N2O5ClI4Cr: C, 21.1; H, 1.8; N,
3.1. Found: C, 21.0; H, 2.0; N, 3.2%. Selected IR bands
(KBr cm1): 1637s, mC@N; 1566w, mC@C; 1372w, mCN;
1391m, mCO; 569w, mCrO; 375w, mCrN. UVVis spectrum
in DMSO [kmax (nm), e (dm3 cm1 mol1)]: 292 (9940),
346 (3410), 415 (2370). le(298 K): 4.03 BM.
2.4. Physical measurements
Elemental microanalyses (C, H, N) were performed by
the Microanalytical Laboratory of the Departamento de
Qumica of the Universidade Federal de Sao Carlos, with
a Faison EA 1108 CHNS-O instrument. Melting points
were determined using a Mel-Temp II Laboratory Devices
USA. The molar conductance was determined with a ColeParmer Model 1481-90 conductivity meter. IR spectra were
recorded in KBr pressed discs (1% by weight) with a
Bomem Michelson 102 FT-IR instrument. The 1H and
13
C NMR spectra of the free ligand in CDCl3 and
DMSO-d6, with tetramethylsilane as an internal standard,
were obtained using a Bruker ARX 400 MHz 9.4 T spectrophotometer. All chemical shifts (1H and 13C) are given
in ppm versus tetramethylsilane (TMS). Magnetic susceptibility measurements were made on a powered sample at
298 K using a JohnsonMatthey Magnetic Susceptibility
Balance model Mark II using the magnetic susceptibility
standard HgCo(NCS)4.
All the mass spectra were performed by the mass spectrometry Laboratory of the Departamento de Qumica of
the Universidade Federal de Sao Carlos using a QuattroLC
triple-quadrupole mass spectrometer (Micromass, Manchester, UK) coupled with an liquid chromatograph; the
data were acquired using Masslynx software (version
3.2). The electrospray ionization capillary voltage was
maintained between 4 and 4.2 kV, and the cone voltage
was kept at 30 V unless otherwise stated. Nitrogen was
used as the desolvation and nebulization gas. The source
and desolvation temperatures were kept at 100 C. The
ESI mass spectra were recorded by scanning MS1. The
mass spectra of these compounds were performed on
15 ng dm3 DMSO solutions.
Electronic spectra were recorded in the 260800 nm
range using a Shimadzu MultSpec-1501 instrument. These
spectra of the DMSO solutions were obtained at room temperature using matched 1.0 cm quartz cells. The electronic
spectra were resolved by deconvolution using the Voigt
function, amplitude, Gaussian/Lorentzian widths, of the
Jandel Scientic Software PeakFit program [42]. In this
version of the Voigt function, the Gaussian and Lorentzian
widths were calculated as well as the amplitude and center
of each peak. The width and area of each peak were
allowed to vary without using aPbackground function.
A
P
reliability factor, dened as R = jyobs.,i  ycalc.,ij/ yobs.,i,
was used to determine the goodness of t between the measured and the calculated spectra. A degree of freedom

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

Fig. 2. Complexes prepared in this study.

Fig. 3. IR spectra (2504000 cm1) of H2L8 and [Cr(L8)(H2O)2]Cl.

usually very strong. The ligands are relatively planar with

adequate intramolecular distance that favors intramolecular hydrogen bond formation [47]. Electron-donating
groups on the phenolic ring increase the electron density
on the hydroxyl oxygen making the HO bond stronger,
the absorption usually appears as a broad band in the IR
spectrum. For the chromium(III) complexes, the disappearance of this band is expected due to the substitution of
hydrogen for the metal on the complex formation.
The C@N stretching frequencies are in the 1592
1640 cm1 region as reported for similar ligands [48,49].
The ligands exhibit the characteristic C@N band in 1630
1646 cm1 region, while the complexes the C@N were
observed in the 16281638 cm1 region. The C@N stretching frequency is generally shifted to a lower frequency,
indicating a decrease in the C@N bond order due to the
coordinate bond of the metal with the imine nitrogen lone
pair [50,51].
In the 15001600 cm1 region, the observed bands
were attributed to aromatic C@C vibrations. On coordi-

nation these bands shift to lower frequencies for the

chromium complexes of ligands H2L1, H2L7 and H2L8
and to higher frequencies for H2L2, H2L3, H2L4 and
H2L6 [52].
The CN stretching frequency has been reported
[5254] in the 13501410 cm1 region. For the free
ligands, the band occurs in the 12901310 cm1region
and for the complexes, 13501390 cm1 region. The
CO stretching frequency appears as a weak band within
the 12901340 cm1 range as reported for similar ligands
[45,46,55]. This band occurs in the 12801300 cm1
region for the free ligands and in the 12901310 cm1
region for the complexes. The CO stretching frequency
is generally shifted to a higher frequency, indicating the
formation of bond oxygen of phenolic group with the
metal ion [50,51].
Evidence regarding the bonding of the chromium with
the nitrogen and/or oxygen atom of the Schi base is provided by the appearance of bands in the 250600 cm1
region. The band at 570590 cm1 is assigned to m(CrO),

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while band at 260390 cm1 is assigned to m(CrN). These

bands are observed as new peaks for the complexes and are
not present in the spectrum of the free ligand. As pointed
out by Percy and Thornton [55], the metaloxygen and
metalnitrogen frequency assignments are at times very
dicult.
3.2. Nuclear magnetic resonance spectra
The 1H NMR spectra of the free ligands were recorded
in CDCl3 and DMSO-d6. The chemical shifts, expressed
in ppm downeld form tetramethylsilane, are given in
Table 1. 1H NMR spectra of similar Schi base ligands
have been reported [40,52,5658]. The free ligands exhibit
a broad peak between 14 and 12.5 ppm, which is due to
hydrogen-bonded phenolic protons. This peak is due to
hydrogen bonded phenolic protons [56,5961] and the
integration is generally less than 2.0 due to this intramolecular hydrogen bonding [40,61,45]. Signals for the
methine protons of the azomethine group, N@C(H)

were observed between 8.4 and 8.2 ppm. In the region

of 7.66.8 ppm were assigned chemical shifts for hydrogen
of the aromatic ring. The alkyl protons @NCH2CH2
N@ were observed between 4.2 and 3.9 ppm. For H2L4,
the signal for the OCH3 group was observed at
3.75 ppm.
The 13C NMR spectra of the free ligands were
recorded in CDCl3 or DMSO-d6. The chemical shifts,
expressed in ppm downeld form tetramethylsilane, are
given in Table 2. Our numbering system follows that of
Fig. 1. The 13C spectra allow an assignment of the peaks
based on 13C shifts in l-oxobis(disalicyldeneiminato) complexes [40,62] and in similar tetradentate Schi base
ligands and their complexes [40,52]. The chemical shifts
for carbon C(8) of @NCH2CH2-N@, were recorded
between 59.7 and 54.2 ppm. The signals for carbon C(7)
from imine group N@C(H) were observed between
166.8 and 165.2 ppm with no noticeable inuence of the
substituent groups. The signal for C(OCH3) of ligand
H2L4 is 55.8 ppm.

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

7.64 (d, J = 2.6, 2H)

7.44 (dd, J = 8.8, J = 2.6, 2H)

a
b
c

6.83 (d, J = 8.8, 2H)

3.91 (s, 4H)

H2L3c

H2L4c

13.13 (s, 1.3H)

(s) 8.31 (s, 2H)

12.72 (s, 1.2H)

8.32 (s, 2H)

7.51
7.23
6.90
3.97

7.26
6.85
6.74
3.95
3.75

(d, J = 2.8, 2H)

(dd, J = 8.8, J = 2.8, 2H)
(d, J = 8.8, 2H)
(s, 4H)

(d, J = 1.6, 2H)

(dd, J =9.6, J = 1.6, 2H)
(d, J = 9.6, 2H)
(s, 4H)
(s,6H)

H2L5a

H2L6a

>12.00
8.75 (s, 2H)

>12.00
8.56 (s, 2H)

8.42
8.07
7.73
4.00

7.80 (d, J = 2.6, 2H)

7.60 (d, J = 2.6, 2H)

H2L
dOH
dN@C(H)
dPh
C4 H
C6 H
dNCH2

(dd, J = 7.6, J = 1.7, 2H)

(ddd, J = 8.3, J = 7.3, J = 1.7, 2H)
(ddd, J = 7.6, J = 7.3, J = 1.1, 2H)
(dd, J = 8.3, J = 1.1, 2H)
(s, 4H)b

(d, J = 3.0, 2H)

(dd, J = 9.5, J = 3.0, 2H)
(d, J = 9.5, 2H)
(s, 4H)
7c

3.98 (s, 4H)

H2 L8a

13.98 (s, 1.1H)

8.29 (s, 2H)

>12.00
8.46 (s, 2H)

7.41 (d, J = 2.4, 2H)

7.16 (d, J = 2.4, 2H)
4.01 (s, 4H)

8.02 (d, J = 2.3, 2H)

7.70 (d, J = 2.3, 2H)
3.95 (s, 4H)

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.

Other chemical shifts are for the aromatic carbons and

depend on the substituent group when compared to ligand
H2L1 with hydrogens on C(3), C(4), C(5), and C(6). The
signal for C(1) bonded to the imine group is observed
between 118.3 and 122.0. This signal is the least aected
by the substituent groups. The largest shift is only
3.4 ppm due the nitro group. The chemical shifts for the
carbon C(2) bonded to the oxygen of the phenolic group
were observed between 167.2 and 155 ppm. The methoxy
group causes the greatest upeld shift of 6.0 ppm and the
nitro group, the greatest downeld shift of 6.2 ppm when
compared to hydrogen as the substituent. This is reasonable since methoxy is an electron donating group and nitro
an electron withdrawing group and both being para to
C(2).
The signal for C(3) varies between 92.6 and 121.2 ppm.
The greatest eect occurs when iodine is bonded to this carbon. The nitro group, which is meta to this position, has
the next largest eect. The presence of the substituent
groups on C(3) and C(5) has a variable eect on the signal
of C(4), which occurs between 119.4 and 149.0. When C (4)
is ortho to methoxy, the signal suers an upeld shift of
12.9 ppm and a downeld shift of 16.7 when ortho to two
iodides in positions 3 and 5. The chemical shifts for the carbon C(5) also suer a wide variation, from 109.4 for Br to
151.9 for MeO. All the substituents aect this signal. The
signal of C(6) is most aected by the methoxy group ortho
to this carbon.
All the substituents aect the chemical shifts of the aromatic carbons. For the mono-substituted ligands, the
methoxy and nitro groups present the greatest inuence.
The methoxy group on C(5) causes a upeld shift of the signals of C(2), C(4), and C(6) and a downeld shift for C(5)
in comparison with the 13C spectrum of H2L1. The nitro
group on C(5) causes a downeld shift of the signals of
C(1), C(2), C(3) and C(5) and an upeld shift for C(4)
and C(6). For the di-substituted ligands, the order of inuence is I > Br > Cl.

or two bands. Bands due to the n ! p* transition of the

C@C and C@N chromophores normally occur between
270 and 300 nm [63]. These bands shift to the red when
the chromophores are in a conjugated system. These are
observed as a shoulder only for H2L6, 289 nm; H2L7,
286 nm; and H2L8, 296 nm. The strong intramolecular
hydrogen bond occurring in the Schi base ligands may
also account in part for the shift of these bands that occurs
between 400 and 440 nm [64]. Molecular orbital calculations indicate that this band in the 400440 nm region is
an n ! p* transition type, involving the promotion of an
electron of the free electron pair on the nitrogen to an antibonding p-orbital of imine group [64]. Another factor to
be considered in the assignment of this transition is its
absence in spectra of the corresponding complex as shown
in Figs. 4 and 5.
The isolated benzene ring exhibits three characteristic
absorptions at 184, 204 and 256 nm; all assigned to p !
p*-type transitions [63]. Substitutions on the ring, by auxochromes and chromophores, shift this band to the red. The
ligand band between 317 and 370 nm is assigned as a
p ! p* transition involving molecular orbitals of C@N
chromophore and the benzene ring [65]. Electron-donating

3.3. Electronic spectra

The electronic spectra of the DMSO solutions of the
free ligands, recorded in the 250800 region, exhibit one

Fig. 4. Electronic spectra (260800 nm) of H2L3 and [Cr(L3)(OH)(H2O)]

in DMSO.

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Fig. 6. Gaussian/Loretzian analysis of [Cr(L2)(OH)(H2O)] for the DMSO

electronic spectrum.
Fig. 5. Electronic spectra (260800 nm) of H2L7 and [Cr(L7)(H2O)2]Cl in
DMSO.

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.

A consistent treatment for the bands is to assign the

band near 15 60017 600 cm1 as the 4B1g ! 4Eg(4T2g) transition; the band at ca. 18 40020 400 cm1 as the 4B1g !
Table 3
Gaussian/Loretzian band components for the visible spectra of the chromium(III)
complexes in DMSO

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

Assignments I, 4B1g ! 4Eg(4T2g); II, 4B1g ! 4B2g(4T2g); III, 4B1g ! 4Eg(4T1g).

Ref. [70].

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4B2g(4T2g) transition and that 20 00023 100 cm1 as the

4
B1g ! 4Eg(4T1g) transition.
3.4. Mass spectra
A preliminary study of ESI mass spectra of the free
ligands and their corresponding complexes gave promising
results. The negative ion ESI mass spectrum of the H2L1
ligand in DMSO showed the ion [MH] at 267 m/z and
for H2L2 the ion [MH] at 425 m/z. The positive ion
ESI mass spectrum of the H2L3 ligand in DMSO presented
the ion [M+H]+ at 338 m/z and for H2L5 the ion [M+H]+ at
359 m/z. For both types of complexes, [Cr(L)(OH) (H2O)]
or [Cr(L)(H2O)2] Cl, the results indicated the presence of
the [Cr(Ln)(DMSO)2]+ ion in DMSO solution. The positive
ion ESI mass spectrum of the [Cr(L1)]+ complex showed an
ion at 474 m/z corresponding to [Cr(L1)(DMSO)2]+; for
[Cr(L2)]+, an ion at 633 m/z, [Cr(L2)(DMSO)2]+; for
[Cr(L3)]+, an ion at 543 m/z, [Cr(L3)(DMSO)2]+ and for
[Cr(L5)]+, an ion at 564 m/z, [Cr(L5)(DMSO)2]+. Such coordination of solvent molecules to the central metal atom in
the ESI process has been reported [69,70]. A detailed study
of the complexes including a study of the daughter ions of
[Cr(Ln)(DMSO)2]+ complex will be undertaken to determine the behavior of fragmentations of these compounds.
4. Conclusions
A series of symmetrical tetradentate Schi bases containing the N2O2 donor set and their corresponding
chromium(III) complexes have been synthesized and spectrally characterized. The same synthetic procedure gives
two series of complexes depending on the amount and rate
of addition of potassium carbonate used to deprotonate the
Schi base. The initial mass spectra study indicates that for
the two series of complexes in DMSO that the same species, [Cr(Ln)(DMSO)2]+ is present.
Acknowledgements
Financial support from the Conselho Nacional de
Desenvolvimento Cientico e Tecnologico, CNPq, and
the Fundacao de Amparo a` Pesquisa do Estado de Sao
Paulo, FAPESP, is gratefully acknowledged. We thank
FAPESP for providing an undergraduate scholarship to
P.E.A. and the CNPq for graduate scholarships to M.P.
dos S. and S.R. We thank Prof. Alzir A. Batista for the
use of the magnetic susceptibility balance and Dr. Gustavo
Von Poelhsitz for his help with these measurements.
References
[1] M. Wang, L.F. Wang, Y.Z. Li, Q.X. Li, Z.D. Xu, D.Q. Qu,
Transition Met. Chem. 26 (2001) 307.
[2] S.D. Dhumwad, K.B. Gudasi, T.R. Goudar, Indian J. Chem. A 33
(1994) 320.

[3] N.N. Gulerman, S. Rollas, H. Erdeniz, M. Kiraj, J. Pharm. Sci. 26

(2001) 1.
[4] K.H. Reddy, P.S. Reddy, P.R. Babu, Transition Met. Chem. 25
(2000) 154.
[5] P. Tarasconi, S. Capacchi, G. Pelosi, M. Corina, R. Albertini, A.
Bonati, P.P. DallAglio, P. Lunghi, S. Pinelli, Bioorg. Med. Chem. 8
(2000) 154.
[6] H. Singh, L.D.S. Yadav, S.B.S. Mishra, J. Inorg. Nucl. Chem. 42
(1981) 1701.
[7] J. Charo, J.A. Lindencrona, L.M. Carlson, J. Hinkula, R. Kiessling,
J. Virol. 78 (2004) 11321.
[8] D.X. West, S.L. Dietrich, I. Thientananvanich, C.A. Brown, A.E.
Liberta, Transition Met. Chem. 19 (1994) 320.
[9] N.K. Singh, S.B. Singh, Indian J. Chem. A 40 (2001) 1070.
[10] V. Mishra, S.N. Pandeya, S. Anathan, Acta Pharm. Turc. 42 (2000)
139.
[11] D. Jamal, M.A. Quaraishi, J. Electrochem. Soc. India 49 (2000) 56.
[12] E.J. Baran, J. Inorg. Biochem. 80 (2000) 1.
[13] F. Velde, I.W.C.E. Arends, R.A. Sheldon, J. Inorg. Biochem. 80
(2000) 81.
[14] X.D. Zhu, C.G. Wang, Y.L. Dang, H.B. Zhou, Z.S. Wu, Z.J. Liu,
D.L. Ye, Q.C. Zhou, Synth. React. Inorg. Met.-Org. Chem. 30 (2000)
625.
[15] M. Kanthimathi, A. Dhathathreyan, B.U. Nair, Chem. Phys. Lett.
324 (2000) 43.
[16] H. Zhang, Y. Zhang, C. Li, J. Catal. 238 (2006) 369.
[17] B. Bahramian, V. Mirkhani, M. Moghadam, S. Tangestaninejad,
Appl. Catal. A 301 (2006) 169.
[18] J. Wen, J. Zhao, X. Wang, J. Dong, T. You, J. Mol. Catal. A 245
(2006) 242.
[19] E. Konig, S. Herzog, J. Inorg. Nucl. Chem. 32 (1970) 585.
[20] K.A. Biedermann, J.R. Landolph, Cancer Res. 50 (1990) 7835.
[21] R.A. Anderson, Regul. Toxicol. Pharmacol. 26 (1997) S25.
[22] W. Mertz, J. Nutr. 123 (1993) 626.
[23] K. Govindaraju, T. Ramasami, D. Ramaswamy, J. Inorg. Biochem.
35 (1989) 127.
[24] K. Govindaraju, T. Ramasami, D. Ramaswamy, J. Inorg. Biochem.
35 (1989) 137.
[25] E.G. Samsel, K. Srinivasan, J.K. Kochi, J. Am. Chem. Soc. 107
(1985) 7606.
[26] E.M. McGarrigle, D.M. Murphy, D.G. Gilheany, Tetrahedron:
Asymmetry 15 (2004) 1343.
[27] N.J. Kerrigan, H. Muller-Bunz, D.G. Gilheany, J. Mol. Catal. A 227
(2005) 163.
[28] Z.K. Li, L. Liang, L. Yang, H. Chen, X.G. Zhou, J. Mol. Catal. A
235 (2005) 108.
[29] W. Adam, F.G. Gelacha, C.R. Saha-Moller, V.R. Stegmann, J. Org.
Chem. 65 (2000) 1915.
[30] M. Bandini, P.G. Cozzi, A. Umani-Ronchi, Angew. Chem., Int. Ed.
39 (2000) 2327.
[31] M. Bandini, P.G. Cozzi, A. Umani-Ronchi, Tetrahedron 57 (2001)
835.
[32] S.E. Schaus, J. Branalt, E.N. Jacobsen, J. Org. Chem. 63 (1998) 403.
[33] M. Malinowska, P. Kwiatkowski, J. Jurczak, Tetrahedron Lett. 45
(2004) 7693.
[34] R. Vijayalakshmi, M. Kanthimathi, V. Subramanian, B.U. Nair,
Biochim. Biophys. Acta 1475 (2000) 157.
[35] V.G. Vaidyanathan, T. Weyhermuller, B.U. Nair, J. Subramanian, J.
Inorg. Biochem. 99 (2005) 2248.
[36] R. Rajaram, B.U. Nair, T. Ramasami, Biochem. Biophys. Res.
Commun. 210 (1995) 434.
[37] R.L. Paddock, S.T. Nguyen, J. Am. Chem. Soc. 123 (2001) 11498.
[38] A.P. de A. Marques, E.R. Dockal, F.C. Skrobot, I.L.V. Rosa, Inorg.
Chem. Commun. (in press).
[39] A.C. Barbosa, M.Sc. Thesis, Universidade Federal de Sao Carlos,
Brazil, 2004.
[40] O. Signorini, E.R. Dockal, G. Castellano, G. Oliva, Polyhedron 15
(1995) 245.

Please cite this article in press as: P.E. Aranha et al., Polyhedron (2006), doi:10.1016/j.poly.2006.11.005

ARTICLE IN PRESS
10

P.E. Aranha et al. / Polyhedron xxx (2006) xxxxxx

[41] S. Yamada, K. Iwasaki, Bull. Chem. Soc. Jpn. 42 (1969) 1463.

[42] Peak Fit v.4.0 Documentation, AISN Software Inc., San Rafael,
CA, 1995, pp. 8-78-9.
[43] Peak Fit v.4.0 Documentation, AISN Software Inc., San Rafael,
CA, 1995, p. B-1.
[44] J.E. Huheey, E.A. Keiter, R.L. Keiter, Inorganic Chemistry Principles of Structure and Reactivity, 4th ed., HaperCollins College
Publishers, New York, 1993, p. 465.
[45] K. Ueno, A.E. Martel, J. Phys. Chem. 60 (1956) 1270.
[46] J.A. Faniran, K.S. Patel, J.C. Bailar Jr., J. Inorg. Nucl. Chem. 36
(1974) 1547.
[47] H.H. Freedman, J. Am. Chem. Soc. 83 (1961) 2900.
[48] A. Vogt, S. Wolowiec, R.L. Prasas, A. Gupta, J. Skarzeviski,
Polyhedron 17 (1998) 1231.
[49] J.R. Zamian, E.R. Dockal, Transition Met. Chem. 21 (1996) 370.
[50] G.A. Kohawole, K.S. Patel, J. Chem. Soc., Dalton Trans. (1981)
1241.
[51] P. Gluvchinsky, G.M. Mocler, Spectrochim. Acta A 32 (1976) 1615.
[52] F.A. Bottino, P. Finocchiaro, E. Libertini, J. Coord. Chem. 16 (1988)
341.
[53] P. Gluvchinsky, G.M. Mocler, E. Sinn, Spectrochim. Acta A 33
(1977) 1073.
[54] X. Wang, X.M. Zang, H.X. Lin, Polyhedron 14 (1993) 293.
[55] G.C. Percy, J. Thornton, J. Inorg. Nucl. Chem. 35 (1973) 35, 2319.
[56] M. Gullotti, A. Pasini, P. Fantucci, R. Ugo, R.D. Gillard, Gazz.
Chim. Ital. 102 (1972) 855.

[57] B.N. Ghose, R.A. Bako, Acta Chim. Hung. 124 (1987) 459.
[58] R.C. Felicio, E.T.G. Cavalheiro, E.R. Dockal, Polyhedron 20 (2001)
261.
[59] C. Condorelli, I. Fragala, S. Giurida, A. Cassol, Z. Anorg. Allg.
Chem. 412 (1975) 251.
[60] N.M.D. Brown, D.C. Nonhebel, Tetrahedron 24 (1968) 5655.
[61] R.M. Silverstein, G.C. Bassler, T.C. Morril, Spectrometric Identication of Organic Compounds, 5th ed., Wiley, New York, 1991, pp.
183184.
[62] K.S. Murray, J. Chem. Soc., Dalton Trans. (1975) 1538.
[63] R.M. Silverstein, G.C. Bassler, T.C. Morril, Spectrometric Identication of Organic Compounds, 5th ed., Wiley, New York, 1991, pp.
110111.
[64] B. Bosnich, J. Am. Chem. Soc. 90 (1968) 627.
[65] S.M. Grawford, Spectrochim. Acta 19 (1963) 255.
[66] L. Dubicki, M.A. Hitchman, P. Day, Inorg. Chem. 9 (1970) 188.
[67] J.E. Huheey, E.A. Keiter, R.L. Keiter, Inorganic Chemistry Principles of Structure and Reactivity, 4th ed., HaperCollins College
Publishers, New York, 1993, pp. 442449.
[68] A.B.P. Lever, Inorganic Electronic Spectroscopy, 2nd ed., Elsevier,
Amsterdam, 1984, pp. 161162.
[69] M.K. Kumar, S. Prabhakar, M.R. Kumar, T.J. Reddy, S. Premsingh,
S. Rajagopal, M. Vairamani, Rapid Commun. Mass Spectrom. 18
(2004) 1103.
[70] V. Katta, S.K. Choudhury, B.T. Chait, J. Am. Chem. Soc. 112 (1990)
5348.

Please cite this article in press as: P.E. Aranha et al., Polyhedron (2006), doi:10.1016/j.poly.2006.11.005