Inorganic Chemistry Communications 9 (2006) 208–211

www.elsevier.com/locate/inoche

A new facile high yield preparative route for mixed-trinuclear

acetate clusters
Heron Vrubel a, Tai Hasegawa b, Elisabeth de Oliveira c, Fábio S. Nunes a,*

a
Departamento de Quı́mica, Universidade Federal do Paraná, Centro Politécnico – C.P. 19081, 81531-990 Curitiba, Parana, PR, Brasil
b
Department of Chemistry, Stanford University, Stanford, CA 94305-5080, USA
c
Instituto de Quı́mica, Universidade de São Paulo, C.P. 26077, 05599-970 São Paulo, SP, Brasil

Received 15 September 2005; accepted 20 October 2005

Available online 13 December 2005

Abstract

The cluster compounds [FeIII3O(CH3CO2)6(H2O)3]CH3COO, [FeIII2FeIIO(CH3COO)6(H2O)3], [FeIII2CoIIO(CH3COO)6(H2O)3],

[FeIII2NiIIO(CH3COO)6(H2O)3], [VIII2FeIIO(CH3COO)6(H2O)3] and [VIII2CoIIO(CH3COO)6(H2O)3 were prepared by new synthetic
routes. Homometallic clusters can be isolated from a clean reaction between the metal hydroxide and acetic acid. The heterobimetallic
compounds were obtained by the reaction of the iron(III) or vanadium(III)-homometallic cluster, in water, with an excess of iron(II),
cobalt(II) and nickel(II) acetates. The new route give pure products with much higher yields when compared with the classical methods.
The compounds were characterized by atomic absorption and elemental analysis, electrochemistry and IR spectroscopy.

2005 Elsevier B.V. All rights reserved.

Keywords: Mixed-trinuclear acetate clusters; New synthetic routes; Infrared; Electrochemistry

Trinuclear oxo-centered acetate complexes have been
extensively investigated as models of electronic and mag-
netic extended interactions [1–4], as homogeneous catalysts
[5] and as important building blocks to supramolecular
chemistry [6].
The iron acetate cluster was first isolated in 1909 by
Weinland and Gussmann [7] although at the time they were
not able to propose the correct formula. The first examples
of mixed metal trinuclear clusters were synthesized by
Weinland and Holtmeier [8], but were not recognized at
the time. Later, Blake and co-workers [9] showed by X-
ray studies that the products from Weinland
s procedures
were in fact trinuclear [FeIII2MIIO(CH3COO)6(H2O)3] spe-
cies (M = Co or Ni).
The classical method to obtain the trinuclear mixed
metal FeIII2MII (M = transition metal ion) clusters consists
in the reaction of a mixture of an iron(III) salt and a diva-
lent metal salt with sodium acetate in aqueous or alcoholic
*
Corresponding author. Tel.: +55 41 33613180; fax: +55 41 33613186.
E-mail address: fsnunes@quimica.ufpr.br (F.S. Nunes).
solution. The method gives yields around 30% and the
product is not always pure, mostly contaminated with
sodium salts.
Herein we present new facile, high yield synthetic routes
to obtain homometallic and heterometallic acetate trinu-
clear clusters like [FeIII3O(CH3CO2)6(H2O)3]CH3COO,
[FeIII2FeIIO(CH3COO)6(H2O)3], [FeIII2CoIIO(CH3COO)6
(H2O)3], [FeIII2NiIIO(CH3COO)6(H2O)3], [VIII2FeIIO(CH3
COO)6(H2O)3] and [VIII2CoIIO(CH3COO)6(H2O)3.
Glossary of compounds: [FeIII3O(CH3CO2)6(H2O)3]CH3
COO (1); [FeIII2FeIIO(CH3COO)6(H2O)3] (2); [FeIII2CoIIO
(CH3COO)6(H2O)3] (3); [FeIII2NiIIO(CH3COO)6(H2O)3]
(4); [VIII2FeIIO(CH3COO)6(H2O)3] (5); [VIII2CoIIO(CH3
COO)6(H2O)3 (6).
All reagents were used as supplied by Aldrich Chemical
Co. When necessary, the operations were carried out under
an inert atmosphere with the use of standard Schlenk tech-
niques or inside a Vacuum Atmosphere glove box equip-
ment. Infrared spectra were obtained with a Biorad
Excalibur series spectrophotometer in the region 4000–
400 cm
1 in KBr pellets. Cyclic voltammetry experiments

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2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.inoche.2005.10.023
 H. Vrubel et al. / Inorganic Chemistry Communications 9 (2006) 208–211
were carried out with a Microquı́mica Potentiostat model
MQPG-01. A platinum disc electrode was employed for
the measurements at I = 0.1 mol L
1 kept constant with
KCl. A Ag/AgCl (KCl 1 mol L
1) and a platinum wire
were used as reference and auxiliary electrodes, respec-
tively. Typical experiments were conducted with 3.0 ·
10
3 mol L
1 aqueous solutions of the complexes at ambi-
ent temperature. Microanalyses were done under nitrogen
by Desert Analytics Laboratories, USA. Metal content
were determined by atomic absorption.
The complexes were prepared as follows: [Fe3O(CH3
CO2)6(H2O)3]CH3COO (1). Equimolar amounts of iro-
n(III) chloride and ammonium hydroxide were mixed. A
brown solid (Fe(OH)3) was filtered, thoroughly washed
with water and dried at 76 C under vacuum with an Abder-
halden pistol. Fe(OH)3 (5.0 g–47 mmol) was suspended in a
mixture of 25 mL acetic acid and 10 mL of water. It was
kept under stirring and mild heating until complete dissolu-
tion of the solid. After, the solution was filtered while still
hot and the solvent removed to dryness under vacuum,
recovering a light-orange solid. The yield was 9.8 g (96%).
[FeIII2FeIIO(CH3COO)6(H2O)3] (2). This mixed valence
complex was prepared by the reaction between compound
1 (5.0 g–7.7 mmol, dissolved in 30 mL of nitrogen-saturated
water) and 6.5 g (31 mmol) of Fe(CH3COO)2 Æ 2H2O dis-
solved in 20 mL of deaerated water. A brown-reddish solid
precipitated after 10 min, collected by filtration, washed
with water and dried under vacuum.Yield was 7.1 g
(89%). [FeIII2CoIIO(CH3OO)6(H2O)3] (3). This heterome-
tallic cluster was prepared dissolving 2.0 g (3.1 mmol) of
complex 1 in 15 mL of hot water and mixing it with 2.0 g
(7 mmol) of Co(CH3COO)2 Æ 4H2O dissolved in 15 mL of
water. The mixture was heated and stirred for 10 min while
most of the product precipitated. After reaching the room
temperature a brown-reddish solid was recovered, washed
with ethanol and dried under vacuum. Yield was 2.3 g
(84%). [FeIII2NiIIO(CH3COO)6(H2O)3] (4). This light-
brown solid was isolated as described for complex 3. Yield
was 2.1 g (77%). [VIII2FeIIO(CH3COO)6(H2O)3] (5).
[V3O(CH3COO)6(CH3OH)3]CH3COO was prepared as
complex 1 in a mixture of 20 mL of acetic acid and 10 mL
of methanol under dinitrogen atmosphere. After, it was
mixed with a solution of Fe(CH3COO)2 Æ 2H2O (2 g–
10 mmol) dissolved in 20 mL of methanol. A dark blue solid
Scheme 1. New routes for homo and heterometallic acetate clusters.
209
was recovered after two weeks, washed with methanol and
dried under vacuum. Yield was 0.91 g (32%). [VIII2CoIIO
(CH3COO)6 (H2O)3] (6). To a solution of [V3O(CH3
COO)6(CH3OH)3] CH3COO was added Co(CH3COO)2 Æ
4H2O (3.0 g–12 mmol) dissolved in 30 mL of water. In a
few minutes, a large amount of a green solid appeared
and was filtered, washed with water, then methanol and
dried under vacuum. Yield was 91% (2.61 g).
The classic procedure current being used to prepare tri-
nuclear-acetate-homometallic clusters [MIII3O(CH3CO2)6
(L)3]+ (L = solvent or a neutral ligand, such as pyridine
or pyrazine) is to mix a M(III) salt, usually nitrate or chlo-
ride in the presence of sodium acetate and acetic acid in
water/ethanol or water/methanol solutions [7–9]. Mixed-
trinuclear acetate clusters [M2M 0 O(CH3COO)6L3] have
been isolated from a similar reaction between M(III) and
M 0 (II) nitrates and sodium acetate. After workup the solid
is frequently isolated with sodium salts impurities, decreas-
ing the yields to as low as 30%.
Our new approach (Scheme 1) for the homo and hetero-
metallic trinuclear compounds were successful showing
yields as high as 96%, much higher when compared with
the classic method that gives several products (a mixture
of M2M 0 , MM 0 2, M3 and M 0 3 complexes) and requires long
chromatographic separation procedures. The synthetic
pathway for the homometallic is a clean one-step acid–base
reaction, producing only water and salt. The exchange
reaction between the homometallic cluster [MIII3O(CH3
CO2)6(L)3]+ and the MII-acetate to produce the mixed
metal cluster is an innovative approach that minimizes
the formation of by-products and in some way contributes
to a better understanding of self-assembly mechanisms.
The elemental analysis (C, H, N and metal content) seen
in Table 1 as well as spectroscopic and electrochemical
(see below) behavior support the trinuclear formulation.
Infrared spectra of complexes 1–6 exhibited the same
pattern. A typical spectrum is shown in Fig. 1, with main
bands at cm
1: 1590 (masym COO
), 1423 (msymCOO), 1350
(sym bend CH3), 1034 (rock CH3), 662 and 618 (in plane
and out-of-plane bend COO
, respectively) and at 563
(mas M3O). The frequency difference between the antisym-
metric and symmetric stretching modes of the carboxylate
group is typical of acetate ligand bridging two metal ions
[10–12]. The redox behavior of the most soluble clusters
210 H. Vrubel et al. / Inorganic Chemistry Communications 9 (2006) 208–211

Table 1
Elemental analysis data for compounds 1-6
Complex %C %H %N %Fe %V %M
1 25.36 (25.83) 3.68 (4.18) 0.23 (0.0) 25.0 (25.74) – –
2 24.11 (24.35) 3.86 (4.10) 0.05 (0.0) 29.0 (28.3) – –
3 23.72 (24.22) 3.71 (4.06) 0.26 (0.0) 18.55 (18.77) – 9.80 (9.90)a
4 23.15 (24.23) 3.98 (4.01) 0.28 (0.0) 18.20 (18.78) – 9.67 (9.87)b
5 28.03 (28.87) 3.88 (4.85) 0.13 (0.0) 9.0 (9.87) 17.40 (18.00) –
6 25.34 (25.32) 3.82 (4.25) <0.05 (0.0) – 17.24 (17.90) 10.12 (10.35)a
Calculated values in parenthesis.
a
%Co.
b
%Ni.

Fig. 2. Cyclic voltammogram of [FeIII2CoII(CH3COO)6(H2O)3] (3) in

Fig. 1. Infrared spectrum of [FeIII2CoII(CH3COO)6(H2O)3] (3) in KBr aqueous solution. Initial cathodic scan.
disc.

was studied. The cyclic voltammograms of the
heterometallic complexes FeCo and FeNi showed a two-
electron reduction wave at
0.32 versus Ag/AgCl with the
probable breakage of the cluster structure (step (a) below)
and two irreversible mono-electronic oxidations of the
resulting fragments at 0.06 and 0.51 V (steps (b) and (c))
(Fig. 2). A similar electrochemical behavior was observed
for the all-iron mixed valence complex [FeIII2FeIIO(CH3
COO)6(H2O)3], suggesting that the electron-transfer pro-
cesses is formally centered at the iron ion.
½FeIII FeIII MII  þ 2e
! ½FeII  þ ½FeII MII 
The route is currently being tested in our laboratory with
second-row transition metals and it was successfully car-
ried out with ruthenium acetate clusters.
Acknowledgments
Fundação Araucária and CNPq supported this work.
H.V. and F.S.N. thanks the Brazilian Research Council
(CNPq) for research fellowships.
ðaÞ References

½FeII  ! ½FeIII  þ e

II II III II
R.D. Cannon, J. Chem. Soc. Chem. Commun. (1994) 1657–1658.
½Fe M  ! ½Fe M  þ e
The analytical and spectroscopic data supported the
new facile, high yield synthetic pathways to homo and het-
erometallic trinuclear acetate compounds. The route
proves to be possible to exchange one metal center from
an already assembled homometallic cluster by another
metal ion in a lower oxidation state. Classic methods to
prepare the clusters by mixing the metal salts make it diffi-
cult to rationalize any self-assembly mechanism. It is worth
to mention that we were unable to exchange two MIII ions.
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