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Inorganic Chemistry Communications 9 (2006) 208–211 www.elsevier.com/locate/inoche A new facile high yield preparative
Inorganic Chemistry Communications 9 (2006) 208–211 www.elsevier.com/locate/inoche A new facile high yield preparative

Inorganic Chemistry Communications 9 (2006) 208–211

Inorganic Chemistry Communications 9 (2006) 208–211 www.elsevier.com/locate/inoche A new facile high yield preparative

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 , Fa´bio S. Nunes a, *

a Departamento de Quı´mica, Universidade Federal do Parana´ , Centro Polite´cnico – C.P. 19081, 81531-990 Curitiba, Parana, PR, Brasil b Department of Chemistry, Stanford University, Stanford, CA 94305-5080, USA c Instituto de Quı´mica, Universidade de Sa˜o Paulo, C.P. 26077, 05599-970 Sa˜o Paulo, SP, Brasil

Received 15 September 2005; accepted 20 October 2005 Available online 13 December 2005

Abstract

The cluster compounds [Fe III 3 O(CH 3 CO 2 ) 6 (H 2 O) 3 ]CH 3 COO, [Fe III 2 Fe II O(CH 3 COO) 6 (H 2 O) 3 ], [Fe III 2 Co II O(CH 3 COO) 6 (H 2 O) 3 ], [Fe III 2 Ni II O(CH 3 COO) 6 (H 2 O) 3 ], [V III 2 Fe II O(CH 3 COO) 6 (H 2 O) 3 ] and [V III 2 Co II O(CH 3 COO) 6 (H 2 O) 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 [Fe III 2 M II O(CH 3 COO) 6 (H 2 O) 3 ] spe- cies (M = Co or Ni). The classical method to obtain the trinuclear mixed metal Fe III 2 M II (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).

1387-7003/$ - see front matter 2005 Elsevier B.V. All rights reserved.

doi:10.1016/j.inoche.2005.10.023

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 [Fe III 3 O(CH 3 CO 2 ) 6 (H 2 O) 3 ]CH 3 COO, [Fe III 2 Fe II O(CH 3 COO) 6 (H 2 O) 3 ], [Fe III 2 Co II O(CH 3 COO) 6 (H 2 O) 3 ], [Fe III 2 Ni II O(CH 3 COO) 6 (H 2 O) 3 ], [V III 2 Fe II O(CH 3 COO) 6 (H 2 O) 3 ] and [V III 2 Co II O(CH 3 COO) 6 (H 2 O) 3 . Glossary of compounds: [Fe III 3 O(CH 3 CO 2 ) 6 (H 2 O) 3 ]CH 3 COO (1); [Fe III 2 Fe II O(CH 3 COO) 6 (H 2 O) 3 ] (2); [Fe III 2 Co II O (CH 3 COO) 6 (H 2 O) 3 ] (3); [Fe III 2 Ni II O(CH 3 COO) 6 (H 2 O) 3 ] (4); [V III 2 Fe II O(CH 3 COO) 6 (H 2 O) 3 ] (5); [V III 2 Co II O(CH 3 COO) 6 (H 2 O) 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

H. Vrubel et al. / Inorganic Chemistry Communications 9 (2006) 208–211

209

were carried out with a Microquı´mica 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: [Fe 3 O(CH 3

was recovered after two weeks, washed with methanol and dried under vacuum. Yield was 0.91 g (32%). [V III 2 Co II O (CH 3 COO) 6 (H 2 O) 3 ] (6). To a solution of [V 3 O(CH 3 COO) 6 (CH 3 OH) 3 ] CH 3 COO was added Co(CH 3 COO) 2 Æ 4H 2 O (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 [M III 3 O(CH 3 CO 2 ) 6 (L) 3 ] + (L = solvent or a neutral ligand, such as pyridine

CO 2 ) 6 (H 2 O) 3 ]CH 3 COO (1). Equimolar amounts of iro-

or

pyrazine) is to mix a M(III) salt, usually nitrate or chlo-

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-

ride in the presence of sodium acetate and acetic acid in water/ethanol or water/methanol solutions [7–9]. Mixed- trinuclear acetate clusters [M 2 M 0 O(CH 3 COO) 6 L 3 ] have

halden pistol. Fe(OH) 3 (5.0 g–47 mmol) was suspended in a

been isolated from a similar reaction between M(III) and

mixture of 25 mL acetic acid and 10 mL of water. It was

M

0 (II) nitrates and sodium acetate. After workup the solid

kept under stirring and mild heating until complete dissolu-

is

frequently isolated with sodium salts impurities, decreas-

tion of the solid. After, the solution was filtered while still hot and the solvent removed to dryness under vacuum,

ing the yields to as low as 30%. Our new approach (Scheme 1) for the homo and hetero-

recovering a light-orange solid. The yield was 9.8 g (96%). [Fe III 2 Fe II O(CH 3 COO) 6 (H 2 O) 3 ] (2). This mixed valence complex was prepared by the reaction between compound

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

1 (5.0 g–7.7 mmol, dissolved in 30 mL of nitrogen-saturated

of

M 2 M 0 , MM 0 2 , M 3 and M 0 3 complexes) and requires long

water) and 6.5 g (31 mmol) of Fe(CH 3 COO) 2 Æ 2H 2 O 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%). [Fe III 2 Co II O(CH 3 OO) 6 (H 2 O) 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(CH 3 COO) 2 Æ 4H 2 O 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%). [Fe III 2 Ni II O(CH 3 COO) 6 (H 2 O) 3 ] (4). This light- brown solid was isolated as described for complex 3. Yield was 2.1 g (77%). [V III 2 Fe II O(CH 3 COO) 6 (H 2 O) 3 ] (5). [V 3 O(CH 3 COO) 6 (CH 3 OH) 3 ]CH 3 COO 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(CH 3 COO) 2 Æ 2H 2 O (2 g– 10 mmol) dissolved in 20 mL of methanol. A dark blue solid

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 [M III 3 O(CH 3 CO 2 ) 6 (L) 3 ] + and the M II -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 ( m asym COO ), 1423 ( m sym COO), 1350 (sym bend CH 3 ), 1034 (rock CH 3 ), 662 and 618 (in plane and out-of-plane bend COO , respectively) and at 563 (m as M 3 O). 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

[10–12] . The redox behavior of the most soluble clusters Scheme 1. New routes for homo

Scheme 1. New routes for homo and heterometallic acetate 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 9.67 (9.87) b

4

23.15 (24.23)

3.98 (4.01)

0.28 (0.0)

18.20 (18.78)

5

28.03 (28.87)

3.88 (4.85)

0.13 (0.0)

9.0 (9.87)

17.40 (18.00)

– 10.12 (10.35) a

6

25.34 (25.32)

3.82 (4.25)

<0.05 (0.0)

17.24 (17.90)

Calculated values in parenthesis.

a %Co.

b %Ni.

Calculated values in parenthesis. a %Co. b %Ni. Fig. 1. Infrared spectrum of [Fe I I

Fig. 1. Infrared spectrum of [Fe III 2 Co II (CH 3 COO) 6 (H 2 O) 3 ] (3) in KBr 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 [Fe III 2 Fe II O(CH 3 COO) 6 (H 2 O) 3 ], suggesting that the electron-transfer pro- cesses is formally centered at the iron ion.

ðaÞ

ðbÞ

ðcÞ

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 M III ions.

½Fe III Fe III M II þ 2e ! ½Fe II þ½Fe II M II

½Fe II Fe III þ e

½Fe II M II Fe III M II þ e

I I M I I !½ Fe I I I M I I þ e Fig.

Fig. 2. Cyclic voltammogram of [Fe III 2 Co II (CH 3 COO) 6 (H 2 O) 3 ] (3) in aqueous solution. Initial cathodic scan.

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

Fundac¸a˜o Arauca´ria and CNPq supported this work. H.V. and F.S.N. thanks the Brazilian Research Council (CNPq) for research fellowships.

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