Polyhedron 24 (2005) 511519 www.elsevier.

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Spectroscopic characterization of coordination complexes based on dichlorocopper(II) and poly(4-vinylpyridine): Application in catalysis
nez a, Paulino Betancourt b, Alvaro J. Pardey a,*, Alcides D. Rojas a, Jorge E. Ya b c d Carlos Scott , CarlosChinea , Caribay Urbina , Deln Moronta e, Clementina Longo
b a n, Escuela de Qu mica, Facultad de Ciencias, Universidad Central de Venezuela, Caracas, Venezuela Centro de Equilibrios en Solucio lisis Petro leo y Petroqu mica, Escuela de Qu mica, Facultad de Ciencias, Universidad Central de Venezuela, Caracas, Venezuela Centro de Cata c mica Organometa lica y Macromolecular, Escuela de Qu mica, Facultad de Ciencias, Universidad Central de Venezuela, Centro de Qu Caracas, Venezuela d a Electro nica, Facultad de Ciencias, Universidad Central de Venezuela, Caracas, Venezuela Centro de Microscop e sica, Facultad de Ciencias, Universidad Central de Venezuela, Caracas, Venezuela Escuela de F f n y Desarrollo de Radiofa rmacos, Facultad de Farmacia, Universidad Central de Venezuela, Caracas, Venezuela Centro de Investigacio

Received 15 June 2004; accepted 8 December 2004

Abstract The formation of transition metal complexes between dichlorocopper(II) and a poly(4-vinylpyridine)/divinylbenzene(2%) polymeric matrix is described in this contribution. The nitrogen atom of the pyridine groups of the organic polymer is coordinatively bonded to the Cu center as suggested by X-ray photoelectron spectroscopy (XPS), UVvis/diuse reectance (UVvis/DR), electron paramagnetic resonance (EPR), dierential scanning calorimetry (DSC) and Fourier transform infrared (FT-IR) techniques. The immobilized catalyst was also characterized by DTA-TGA analysis and the morphology and elemental analysis of this copper/ poly(4-vinylpyridine) complex were studied by the scanning electron microscopy/energy dispersive X-ray (SEM/EDX) technique. This material catalyzes the water gas shift reaction as well as the reduction of nitrobenzene to aniline and azobenzene. 2005 Elsevier Ltd. All rights reserved.
Keywords: Copper; Poly(4-vinylpyridine); Carbon monoxide; Water gas shift reaction; Spectroscopic characterization

1. Introduction The characterization of ion-containing polymers has been the subject of numerous investigations. It has been demonstrated that the themophysical properties of polymeric ligands can be modied by coordination to transition metal complexes [1,2]. The CuCl2 2H2O salt is an attractive candidate to form coordination complexes with the pyridine moieties of poly(4-vinylpyridine). For example, a soluble
Corresponding author. Tel.: +58212 605 1225; fax: +58212 481 8723. E-mail address: apardey@strix.ciens.ucv.ve (A.J. Pardey). 0277-5387/$ - see front matter 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.poly.2004.12.014
*

Cupyridine complex of the type CuCl2(py)2 complex is known [3]. Studies in our laboratories have long been concerned with the use of the rhodium (I) complexes [Rh(COD)(amine)2](PF6) (amine = pyridine, 2-picoline, 3-picoline, 4-picoline, 3,5-lutidine or 2,6-lutidine) immobilized on poly(4-vinylpyridine)/divinylbenzene(2%) as catalyst precursors for various chemical reactions (namely, water gas shift reaction (WGSR) [4,5], reduction of nitrobenzene [6,7] and hydroformylation of 1-hexene [8,9]) due to their easy preparation, good stability and high or moderate catalytic activities. The granular nature of this polymer and its insolubility in all organic solvents allows for it isolation by simple ltration [10].

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We previously reported the homogenous catalysis of the WGSR by copper dichloride dissolved in aqueous substituted pyridine (methyl and dimethyl pyridines) solutions [11]. For example, TF(H2) of about 6 mol/ day for [Cu] = 20 mM (2.0 104 mol), P(CO) = 1.9 atm at 120 C was observed for the more active 4-picoline (4-methylpyridine) system. In the course of continuing to explore similar systems in our laboratories it became a matter of interest to study the Cu/P(4-VP) system because it is known that the most commercial active heterogeneous system catalyst for the WGSR contains a mixture of copper and zinc oxide [12]. In the present study, we extend the use of the poly(4-vinylpyridine)/divinylbenzene(2%) polymeric matrix instead of pyridine as a ligand coordinated to CuCl2 salt. Here, we report the preparation, the characterization by XPS, UVvis/DR, EPR, DSC, FT-IR, DTATGA and SEM/EDX techniques and the catalytic activity of P(4-VP)-immobilized CuCl2 on the water gas shift reaction and the reduction of nitrobenzene.

Photoelectron spectra of the solid were recorded with a VG-220i-XL ESCALAB spectrometer using monochromatized X-ray Mg Ka radiation (1235.6 eV). The solid was mounted on a standard sample stud. Nominal resolution was measured as full-width at half-maximum of 1.0 (core-level spectrum) to 1.5 eV (survey spectrum). The analyzed core-level lines were calibrated against the C 1s binding energy set at 285 eV of CHx neutral carbon. The signals were deconvoluted using mixed GaussianLorentzian curves where the Gaussian character was set at 80%. Since the Cu2p line is rather insensitive to the oxidation state of copper (the Cu 2p3/2 component is at: 932.6, 932.5, 933.7 and 935.1 eV for Cu, Cu2O, CuO and Cu(OH)2, respectively), it is important to follow the energy position of the LMM Auger line of Cu. Gas samples analyses from catalytic runs were performed as described in detail previously [4] on a HewlettPackard 5890 Series II programmable (ChemStation) gas chromatograph tted with a thermal conductivity detector. The column used was Carbosieve-B (80100) mesh obtained from HewlettPackard using a He/H2 mixture as the carrier gas. 2.3. Complex preparation A mixture of 0.5 g of P(4-VP) and 0.0341 g (2.0 104 mol) of CuCl2 2H2O dissolved in 10 mL of 80% aqueous 2-ethoxyethanol was stirred for 72 h in air until about 99% of the copper was extracted by the polymer from the solution as determined by UVvis spectrophotometry. The amount of the absorbed copper on P(4-VP) was determined by subtracting the initial amount of copper salt from the unabsorbed one. The resulting blue polymer was ltered, washed with 5 mL of 2-ethoxyethanol/H2O 8/2, v/v, and dried in vacuum at room temperature. This material will be referred herein as Cu/P(4-VP). 2.4. Catalyst testing WGSR catalytic runs were conducted in all-glass reactor vessels consisting of a 100 mL round bottomed ask connected to an O ring sealed joint to a twoway Rotoow Teon stopcock attached to the vacuum line [4]. In a typical run, the loaded polymer beads and 10 mL of 80% aqueous 2-ethoxyethanol were added to the glass reactor vessel, then the solution was degassed by three freezepumpthaw cycles. The reaction vessel was charged with a CO/CH4 mixture at the desired CO partial pressure (1.4 atm at 25 C, but 1.9 atm at 110 C), and then suspended in a circulating thermostated glycerol oil bath set at 110 C for 848 h. The specied temperature was maintained at 0.5 C by continuously stirring the oil bath as well as the reaction mixture which was provided with a Teon-coated magnetic stirring bar. Gas samples (1.0 mL) were ana-

2. Experimental 2.1. Materials 2-Ethoxyethanol (Aldrich) was distilled from anhydrous stannous chloride. Water was doubly distilled. Poly(4-vinylpyridine)/divinylbenzene(2%) (P(4-VP)), was used as provided by Reilly Industries. Nitrobenzene (Aldrich) was distilled in H2SO4 (1 M) and redistilled from CaCl2 prior to use. All gas mixtures He/H2 (91.4%/8.6%, v/v), CO/CH4 (95.8%/4.2%, v/v) and CO/ CH4/CO2/H2 (84.8%/5.1%/5.3%/4.8%, v/v) were purchased from BOC Gases and were used as received. Dichlorocopper(II) salt (Merck) was used as received. 2.2. Instrumentation The UVvis spectra of the solutions (1 cm quartz cell) and of the solids (Labsphere RSA-PE-20 diuse reectance cell) were recorded on a PerkinElmer Lambda 10 spectrophotometer. Infrared spectra were recorded on a PerkinElmer 1760X-FT spectrophotometer using KBr pellets for solid samples. Electron paramagnetic spectroscopy experiments were carried out in a conventional Varian E-line X-band spectrometer, using a rectangular cavity operating in the TE 102 mode. The scanning electron micrographs were recorded on a Hitachi S-500 microscope with an energy dispersive X-ray detector. The thermal behavior studies were carried out using a TA Instruments SDT 2960 Simultaneous DTA-TGA analyzer. Glass transition temperatures were measured on a PerkinElmer DSC 7 at a rate of 20 C/ min under a nitrogen purge.

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lyzed by GC at the end of the reaction time. Methane was used as internal standard to allow calculation of absolute quantities of CO consumed and H2 and CO2 produced during a time interval, with calibration curves being prepared periodically for CO, CH4, H2, and CO2, and analyzing known mixtures checked their validities. Nitrobenzene reduction catalytic runs were conducted in a 150 mL mechanically stirred stainless steel Parr reactor. In a typical run, 0.5 g of the Cu/P(4-VP) solid, 10 mL of 80% aqueous 2-ethoxyethanol and 1.2 mL (8.1 103 mol) sample of nitrobenzene were added to the reaction vessel. Subsequent to the addition of nitrobenzene, the Parr reactor was charged with the CO/CH4 mixture (27.2 atm partial CO pressure at 150 C) and placed in the oil bath at 150 C for 472 h. After a given time, the reaction was stopped, the reactor cooled to room temperature and excess pressure was vented and products analyzed by GC and GC MS. A response factor method for the GC analyses of the aniline was employed [13]. The GCMS of the aniline (molecular ion peak at m/e = 93 and base peak at m/e = 65) and azobenzene (molecular ion peak at m/e = 182 and base peak at m/e = 77) products is similar to a pure sample of aniline and azobenzene, respectively. Also the organic products were separated by column chromatography and analyzed by 13C and 1H NMR in a Jeol Eclipse 270 NMR spectrometer.

solubility in water. They observed the formation of tetrapyridineCu(II) complexes, [CuL4]2+ (L = a nitrogen atom of the P(4-VP)). Coordination of the nitrogen atom of the pyridine moiety to the Cu(II) center was proposed. Also, G. Jeschke, provided for this soluble copper (II) complex of poly(4-vinylpyridine) a model for the geometry of the rst coordination sphere supported by a combination of EPR, electron-nuclear double resonance methods (ENDOR) and molecular modelling techniques, and found that the structure of this copper complex derives from the propeller structure of Cu(pyridine)4 mainly by rotation of the ligand pyridine rings with a modest tetrahedral distortion [15]. On the other hand, the addition of 2% of divinylbenzene to the poly(4-vinlypyridine) polymer makes the latter insoluble in water and in all organic solvents. In this section, the results of SEM/EDX, UVvis/DR, EPR, FT-IR, XPS, DTA-TGA and DSC techniques, which were used to determine the nature of the water insoluble CuCl2/P(4-VP)/divinylbenzene(2%) immobilized species, are discussed. The SEM with energy dispersive X-ray (EDX) technique was used for studying the morphology of the solid samples. We previously reported a SEM micrograph of a P(4-VP) sample, from which it can be observed that the P(4-VP) is formed by agglomerates of grains with a smooth surface [6]. Fig. 1 corresponds to the micrograph of the solid product of the reaction of P(4-VP) with the CuCl2 2H2O salt in contact with 80% aqueous

3. Results and discussion 3.1. General aspects Dissolution of a solid sample of CuCl2 2H2O (0.0341 g, 2.0 104 mol) in 10 mL of 80% aq. 2-ethoxyethanol at room temperature leads to the gradual formation of a greenblue solution. This solution in contact with 0.5 g of P(4-VP) under continuous stirring for 72 h in air at room temperature gradually leads to formation of a blue solid material and a colorless solution. After charging the mixture formed by the Cu/P(4-VP) ([Cu] = 2.5 wt%) blue solid and 10 mL of 80% of aqueous 2-ethoxyethanol with CO (1.9 atm) and heating the reaction vessel and its content at 110 C in a glycerol bath, the blue solid rst changed to a light-blue color, then (over 15 min) to a yellow color and to a nal light browngreen color, characteristic of the mature catalyst system. The solution above the light browngreen solid remains uncolored. 3.2. Characterization studies Kirsh et al. [14] reported the characterization by EPR and UVvis spectroscopies of the water-soluble CuCl2/ P(4-VP) system. The P(4-VP) employed in their study was not cross-linked with any copolymer, allowing its

Fig. 1. Scanning electron micrograph of the Cu/P(4-VP) fresh catalyst sample. Magnication 5000.

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2-ethoxyethanol after 72 h of stirring in air. The elemental analysis revealed Cu and Cl in the etched areas. The same type of analysis of the smooth regions, whose morphology had not been modied, did not show the presence of Cu and/or Cl. The observed modications in some areas on the surface of the polymeric insoluble ligand can be attributed to the anchoring of the Cu(II) center to the P(4-VP). The UVvis spectrum of CuCl2 2H2O dissolved in 80% aqueous 2-ethoxyethanol and the UVvis/DR spectrum of the Cu/P(4-VP) blue solid sample show the displacement of the dd transition band from 246 to 384 nm after the immobilization process. The signicant dierence in the dd transition bands between the solution and the solid would be a consequence of a dierent coordination environment around copper (II). Eorts to obtain the UVvis/DR spectrum of the Cu/P(4-VP) light browngreen solid were unsuccessful inasmuch that this solid undergoes oxidation to produce the blue cupric polymer-complex during the handling procedures. However, the fact that the used catalyst has a light brown green color suggested that Cu(II) is the predominant oxidation state. It has been stated that Cu(I) complexes would be colorless since dd electronic transitions are not feasible to take place in a d10 system, and metalto-ligand charge transfer possible for d10 complex with aromatic structure also does not occur in the visible region of the spectrum [16]. EPR experiments show signals (Fig. 2(a)) for the Cu/ P(4-VP) ([Cu] = 2.5 wt%) fresh catalyst (blue-colored solid) and these indicate the presence of copper(II) d9 paramagnetic species in this system as expected. Similar EPR behavior was observed on reaction of CuCl2 2H2O

(a)
b

g =2.219
c

g = 2 .334 g = 2.476
a

g =2.106
d

g = 2.003

(b)

H = 100 Gauss

Fig. 2. EPR spectra in the 25003500 G region of: (a) Cu/P(4-VP) fresh catalyst; (b) Cu/P(4-VP) used catalyst.

with 4-picoline and 2-picoline [11]. Fig. 2 also shows the EPR spectrum of the used catalyst (light browngreen colored solid) of the same system (b) in the presence of CO. The EPR result is similar to the one observed for the Cu/P(4-VP) (blue-colored solid) system mentioned above. The samples of both did not have the same amounts of Cu/P(4-VP) as a result of handling procedures. In spite of that, the amplitude of both spectra are the same, the amount of the fresh catalyst sample (blue solid) is roughly half that the used catalyst (light browngreen solid). For that reason the intensity of spectrum (a) is smaller than the other spectrum. However, the widening of the spectrum (a) is larger than spectrum (b). The observed strong EPR signal in the used catalyst indicates the presence of copper(II) d9 species, even though this solid was formed under CO/H2O mixture at the working temperature. Under these reaction conditions the expected reduction of Cu(II) d9 paramagnetic species to Cu(I) d10 non-paramagnetic species by the CO/H2O mixture (as reported in the homogeneous CuCl2/aqueous 4-picoline or 2-picoline systems under CO [11]) was not observed. In spite of the presence of the Cu(II) d9 species at high concentration in the light browngreen solid, both spectra are dissimilar due to dierent molecular environments that surround the Cu(II) center in both solids. Based on these EPR results it is reasonable to propose the existence of at least two kinds of Cu(II) species in the blue-colored fresh catalyst. Under the CO/H2O mixture at the working temperature, one of the Cu(II) species is relatively easily reduced to Cu(I) and the other Cu(II) species remains unreduced. Pomogailo and Golubeva [17] carried out magnetic susceptibility measurements and EPR spectroscopy to study the distribution of cupric ion attached to a polyethylene-grafted poly(acrylic acid) support (PE-grPAA). Their EPR studies revealed changes in the form of the EPR spectrum upon increasing the copper concentration in the PE-gr-PAA matrix. For example, a broad asymmetric singlet is observed which increases steadily in intensity as well as in width with increasing copper(II) content. These data indicate the proximity of the structure of Cu(II) polymer-complexes and also suggests the existence of an increase in dipoledipole interactions between them. The temperature dependence of the magnetic susceptibility as a function of copper content also supports the conclusion of the existence of three types of copper(II) complexes: (1) isolated complexes (type-I) (2) complexes bonded by dipoledipole interactions (type-II) and (3) clusters with strong exchange interactions (type-III). The observed narrowing in the width of the hyperne bands with decreasing Cu(II) content (due to its reduction to Cu(I) by the CO/H2O couple) seen in the EPR spectrum (b) of our Cu(P-4VP) system is probably due to the existence of the same type of dipole-dipole inter-

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action between copper centers described by Pomogailo and Golubeva (type-II complexes). Also our EPR results include the existence of isolated Cu/P(4-VP) complexes (type-I complexes). However, the copper concentration (2.5 wt%) used in our studies is not high enough to form clusters with strong exchange interactions (type-III complexes). The study of the magnetic susceptibility of this Cu/P(4-VP) system, which constitutes an appropriate method for determining the copper valence will be explored in future investigations. The FT-IR spectrum (KBr pellet) of a P(4-VP) sample shows one CN ring stretching band (nCN) at 1596(m, broad) and side group absorption bands (CC ring stretching vibrations) at 1554(m), 1493(m), 1449(m) and 1415(m, broad) cm1. On the other hand, the FT-IR spectrum of fresh prepared KBr pellets of CuCl2/P(4-VP) ([Cu] = 2.5 wt%) also shows the same bands, but three of them (1596, 1493 and 1449 cm1) shifted by ca. +3 cm1. The slight blue shift observed in the nCN of Cu/P(4-VP) could indicate N-coordination of the P(4-VP) polymer to the metal [2,16,18]. Unfortunately, a comprehensive molecular explanation is not available. After charging the Cu/(P4-VP) blue solid with CO atmosphere (1.9 atm) in contact with 10 mL of 80% aqueous solution of 2-ethoxyethanol and heating the reaction vessel in a 110 C glycerol bath for 6 h, the blue solid changed to a light browngreen color characteristic of the mature catalyst system. The FT-IR spectrum (KBr pellets) of the light browngreen color mature Cu/P(4-VP) catalyst sample shows one band in the mCO region at 2068 cm1 (carbonyl-linear Cu species) suggesting the presence of a single carbonyl copper species [11] anchored to the nitrogen-functionalized polymer. Also, the infrared spectrum of the light browngreen solid shows the mCN band at 1598 cm1 and the side group absorption bands (CC ring stretching vibrations) at 1556(m), 1495(m), 1451(m) and 1415(m, broad) cm1. A slight blue shift of ca. +2 cm1 in the mCN and the side group absorption bands is observed. However, the presence of the coordinated-CO decreased the blue shift due to the back-bonding donation of dp atomic orbital of the Cu to the p*-antibonding molecular orbital of the CO, which leads to a competition for electronic density with the p-bonding molecular orbitals of the pyridine ring. Further, a band at 3385 cm1, characteristic of the coordinated OH group, is observed in both blue and light browngreen solid samples. Table 1 shows the XPS data for the fresh (blue solid) and used (light browngreen solid) catalysts. The N1s spectrum for free P(4-VP) features a symmetric peak at 399.0 eV. However, the N1s peaks of the fresh and used catalysts are broader and more asymmetric than the one for free P(4-VP), and each peak can be deconvoluted into two peaks, with one at 399.0 eV and the other at 400.3 eV. The peak at 400.3 eV indicates that a frac-

Table 1 XPS data for fresh (blue-colored solid) and used (light browngreen colored solid) catalysts XPS peak Binding energy (eV) Fresh catalyst N1s O1s Cl2p C1s Cu2p3/2 CuLMM 399.0, 400.3 529.4, 530.4, 531.1 198.0 285.0, 285.9 933.8 569.6 Used catalyst 399.0, 400.3 529.4, 530.4, 531.1, 532.0, 533.1 285.0, 284.9 932.5 567.8

tion of the pyridine nitrogen of the P(4-VP) interacts with the copper cations. Two C1s intense peaks are present in the fresh and used catalyst. The rst (the main peak) at 285.0 eV, is attributed to the aliphatic carbons of adsorbed contaminants, and the second peak at 285.9 (fresh catalyst) and 284.9 eV (used catalyst) is attributed to carbon linked to the nitrogen atom of the pyridine heterocyclic [19]. The XPS spectrum of the fresh Cu/P(4-VP) catalyst shows Cu2p3/2 and CuLMM peaks at 933.8 and 569.6 eV, respectively, in conjunction with intense shake-up features around 938945 eV, which are assigned to Cu(II)OH species [20]. On the other hand, the Cu2p3/2 component for the used Cu/P(4-VP) catalyst shows a sharp peak at 932.5 eV and there is no sign of the shake-up features around 938945 eV, within the detection limits of the XPS technique, and these results suggest the presence of Cu(I) as expected (vide supra). Also, a peak at 567.8 eV was observed, which is typical of metallic copper. It is well known that Cu(I) complexes disproportionate rapidly at ambient temperature to Cu(II) and Cu(0) [21]. Further, the XPS analysis showed O1s lines, for both fresh and used catalyst. The fresh solid presents peaks at 529.4, 530.4 and 531.1 eV, which could be assigned to Cu(II)O species (e.g., CuOH). The O1s peak of the used catalyst is less intense than in the case of the fresh solid. Two additional signals are observed, at 532.0 and 533.1 eV, which could be due to CO (coordinated to Cu) and to water, respectively. Finally, a XPS peak at 198.0 eV (Cl2p) reveals the presence of chloride that is coordinated to the copper in the fresh catalyst. The atomic ratios IN/ICu = 2.5, IO/ICu = 1 and ICl/ ICu = 1 for the fresh catalyst were calculated from the XPS-peaks intensity ratios using the Scoeld cross-section relative to each core level [22]. In such calculations it is assumed that the transmission factor T of the spectrometer and the mean free electron path k are both functions of the kinetic energy, K.E., of the considered photoelectron [23]. The value of 2.5 for the N/Cu ratio indicates that there are at least two dierent Cu/P(4-VP) species; one with two and another with three N atoms bonded to the Cu.

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Further, the DTA-TGA data (Fig. 3) show that the Cu/P(4-VP) complex is stable at 250 C, however a weight loss was observed around 100 C due to the moisture content coming from the preparative method. The dierential scanning calorimetry (DSC) technique was used to determine the glass transition temperatures. The poly(4-vinylpiridine)/2% cross-linked polymer, which exhibits a glass transition temperature (Tg) at 127.1 C, Tg increases by 23.6 C after the immobilization of 2.5 wt% of Cu(II) as the CuCl2 2H2O salt. The produced polymeric coordination complex exhibits a synergistic thermal property and it is related to the coordination of the pyridine moieties of P(4-VP) on the coordination sphere of the Cu(II) center. The pyridine, which is classied as a strong base, can displace one or two water molecules from CuCl2 2H2O and occupy the vacant coordination site on the Cu. Hence is it possible that the Cu bridges two dierent polymer chains via coordination to the pyridine lone pair, forming coordination crosslinks as suggested by the XPS results. Therefore, hindered mobility of this nature provides a way for the enhancement in the Tg. It is noteworthy that the enhancing of the glass transition temperature of poly(4-vinylpyridine) after coordination to ruthenium [2] and osmium [24] complexes has been reported.

3.3. Proposed structures for Cu/P(4-VP) complexes The UVvis, EPR, FT-IR, XPS and DSC results constitute experimental evidences for the formation of a coordination complex between the nitrogen electron lone pair on the P(4-VP) and the copper center in the CuCl2 salt. Based on these spectroscopic results, we therefore, propose the following structures (Scheme 1). The blue-colored solid contains Cu(II) species. On the other hand, the light browngreen colored solid contains Cu(II) and Cu(I) species. The Cu(I) species present in the used catalyst comes from the reduction of the Cu(II)
(a) (b)

N Cu

N N Cl Cu N OH

Cl

OH

Scheme 1. Proposed Cu(II) structures in the fresh catalyst.

Fig. 3. DTA-TGA curves for the Cu/P(4-VP) fresh catalyst sample.

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by the CO/H2O couple under the catalytic conditions. The ligands coordinated to the Cu(II) d9 center of the blue-colored solid are Cl, vinylpyridine and (OH), the last one coming from the hydrolysis of the pyridine residues of P(4-VP). The structures (a) and (b) correspond to the blue solid. The structure (a) has two vinylpyridine groups and the structure (b) has three vinylpyridine groups coordinated to the Cu and this assignment is supported by the EPR and XPS results. Also, two and three-coordination of a metal transition ion by coordinating P(4-VP) is well known [2,25]. McCurdie and Belore proposed the concept of coordination crosslinks for a metal acting as a bridge between pyridine ligands of two dierent polymer chains [2]. Based of the DSC results it is likely probable that the Cu(II) species (a) and (b) are coordinated in a crosslink fashion through the polymeric matrix. The number of vinylpyridine groups coordinated to Cu(II) and Cu(I) species in the light browngreen colored solid is not known although the Cu(II) and Cu(I) species present in this solid must contain OH and CO, and OH ligands, respectively. The last assignment is supported by the FT-IR and XPS results. Although, there is no direct evidence to point which of the two (a) and (b) copper(II) species of the blue solid is reduced to Cu(I), which further by ligand exchange reaction coordinates a CO molecule. However, Gagne et al. [26] reported the reaction of carbon monoxide with blue Cu(LBF2) solution at 25 C (LBF2 = [diuoro-3,3 0 trimethylenedinitrilo-bis(2-butanone oximato)borate]), yielding a yellow solid. The IR and the X ray structure of this yellow solid show a mCO band at 2068 cm1 and a single monocarbonyl copper(I) with a 20-electron count for the metal atom coordinated to ve two-electron donors, Cu(LBF2)(CO). Accordingly, the similarity in the value of the mCO band (2068 cm1) for both Cu(I) CO/P(4-VP) and Cu(LBF2)(CO) solids and the absence of an XPS chlorine signal on the Cu(I)CO/P(4-VP) points to propose that the copper(II) species (b) is reduced to Cu(I) by the CO/H2O couple followed by a substitution of the Cl ligand by a CO molecule yielding a ve coordinated [P(4-VP)xCu(OH)(CO)] (x = 3) immobilized species with three vinylpyridine groups (x) bonded to the Cu(I). The structures (a) and (b) that we proposed for this water insoluble Cu(II)/P(4-VP) system are dierent from the one proposed for the water soluble copper(II) complex of poly(4-vinypyridine) described at the beginning of Section 3.2. Applications of molecular modelling techniques for our water insoluble system are in progress and their results will be published in a forthcoming paper. 3.4. WGSR catalysis The copper immobilized complex ([Cu] = 2.5 wt%) in contact with 10 mL of 80% aqueous 2-ethoxyethanol

generates a system that shows low catalytic activity for the (WGSR equation (1)) at 110 C under P(CO) = 1.9 atm. Quantitative analysis of gas samples taken after the reaction solution reached working temperature, indicated that production of H2 and CO2 and consumption of CO follow the stoichiometry shown in Eq. (1). The eect of the reaction time on the WGSR catalytic activity was studied. Blank experiments revealed that no WGS reaction occurred in the absence of the catalyst. The activities dened as turnover frequency (turnover frequency (gas) = [(mol of gas)/(mol of Cu) (rt)] 24 h, where (rt) is the reaction time in hours) are summarized in Table 2. It is seen that the reaction time variation has no inuence on the TF(H2) and TF(CO2) values. Also the WGS catalytic activity displayed by this Cu/P(4-VP) system is similar to that showed by the homogeneous CuCl2/amine system described above, under comparable reaction conditions. The catalysis of WGSR by this Cu/P(4-VP) system probably goes through a mechanism similar to that proposed for the Rh(4-picoline)2/P(4-VP)/aqueous 2-ethoxyethanol system [27]. The immobilized carbonyl copper(I), Cu(I)CO/P(4-VP), species formed under the catalytic conditions plays an important role as a reaction intermediate in the catalytic cycle (namely, it must be subject to nucleophilic attack by water to generate a hydroxycarbonyl copper species, which eventually through successive transformations leads to CO2 and H2 WGSR-products). CO H2 O
CO2 H2 3.5. Nitrobenzene reduction catalysis Immobilized transition metal complexes into polymers combine the good activity, selectivity and reproducibility typical of homogeneous catalysts with the easy product separation and catalyst recovery characteristic of heterogeneous catalysts [2830]. 1

Table 2 WGSR by CuCl2 2H2O immobilized on P(4-VP) in contact with 80% aqueous 2-ethoxyethanola Reaction time (h) 8 12 18 24 48 H2b (mol 104) 4.5 6.6 10.2 14.6 29.2 CO2b (mol 104) 4.7 7.1 10.5 14.0 28.2 TF(H2)c 6.8 6.6 6.9 7.2 7.3 TF(CO2)c 7.1 7.0 7.0 7.1 7.0

a 0.5 g of P(4-VP), 8 mL of 2-ethoxyethanol, 2 mL of H2O, [Cu] = 2.0 104 mol, (2.5 wt%), P(CO) = 1.9 atm at 110 C. b Based on the gas formed after a given time. c Turnover frequency (gas) = [(mol of gas)/(mol of Cu) (rt)] 24 h, where (rt) is the reaction time in hours. Experimental uncertainty ca. 15%.

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CuCl2 2H2O immobilized on P(4-VP) in contact with 80% aqueous 2-ethoxyethanol mainly catalyzes the reduction of nitrobenzene to aniline (98%) (Eq. (2)) and additionally produces a minor amount of azobenzene (2%), under water gas shift reaction conditions. In addition, hydrogen gas from the WGSR was not detected at the end of the reduction process. The turnover frequencies for aniline production were calculated as mol of aniline per mol of CuCl2 2H2O in 24 h (TF(aniline) = [(mol of aniline)/(mol of Cu) (rt)] 24 h). The calculated catalytic activity dened as TF(aniline) was reproducible to ca. 15% for a series of experimental runs. Furthermore, control experiments show that no reaction was detected in the absence of the polymerimmobilized Cu complex. The data obtained from these studies are reported in Table 3. It is seen that the reaction time variation has a slight inuence on the TF(aniline) values and that change can be associated with the slight shift to the basic zone on the pH nal value of the catalytic mixture due to the increase of the amount of the aniline product (Brnsted base) with time. Reduction of nitrobenzene (1.2 mL) to aniline or other organic products [31] by this Cu/P(4-VP) ([Cu] = 2.5 wt%) system in contact with 10 mL of 80% aqueous 2-ethoxyethanol were not observed under the mild reaction conditions (P(CO) = 1.9 atm at 110 C) previously employed in the catalysis of the WGSR above described, but under the severe reaction conditions (P(CO) = 27.2 atm at 150 C) summarized in Table 3. The nitrobenzene catalytic activities displayed by this Cu/P(4-VP) system are lower than those shown by the immobilized Rh(amine)2/P(4-VP) system [6]. A TF(aniline)/24 h value = 53 (0.65 mmol of aniline formed after 3 h (25% conversion)) was observed under the following reaction conditions: 0.5 g of polymer, 0.26 mL of nitrobenzene, 8 mL of 2-ethoxyethanol, 2 mL of H2O, [Rh] = 2.0 wt%, P(CO) = 0.9 atm at 100 C and [nitro-

benzene]/[Rh] = 25 for the most active amine (2-picoline) system. Further, the reduction of nitrobenzene to aniline by this Cu/P(4-VP) catalyst system probably occurs through a mechanism similar to that proposed for the Rh(2-picoline)2/P(4-VP)/aqueous 2-ethoxyethanol system [7]. The immobilized carbonyl copper(I), Cu(I) CO/P(4-VP), species formed under the catalytic conditions plays an important role as reaction intermediate in the catalytic cycle (namely, a cycloaddition of the nitro group to the CuCO bond followed by elimination of CO2 should lead to the formation of the copper nitrosobenzene [Cu(g2ONR)]+ species, which eventually through successive transformations leads to aniline and azobenzene production). Unfortunately, the concentration of Cu(I)CO/P(4VP) species formed under the catalytic conditions is small as seen from the EPR studies described above. Perhaps this is the reason for the low catalytic activity observed for both WGSR and nitrobenzene reduction. Finally, analyses of the eects of varying the CO pressure, Cu content and temperature on the activity of this Cu/P(4-VP) catalytic system, which are important parameters for the nitrobenzene reduction, are in progress and they will be reported elsewhere. C6 H5 NO2 3CO H2 O ! C6 H5 NH2 3CO2 3.6. Recycling of the anchored catalyst The recycling eciency of the CuCl2/P(4-VP) catalyst was studied in the reduction of nitrobenzene. The results are in Table 4. A change of the catalytic activity was observed after a second use. The above results show that the polymer-anchored catalyst does not have high stability. It is recognized that most Cu(I) complexes are air sensitive. Perhaps, during the recycling process the system was contaminated with air even though care was taken to avoid that. 2

Table 3 Nitrobenzene reduction by CuCl2 2H2O immobilized on P(4-VP) in aqueous 2-ethoxyethanola Reaction time (h) 4 8 12 18 24 72
a

Anilineb (mol 104) 1.9 4.2 7.5 16.6 38.8 58.9

pH nal 7.23 7.27 7.30 6.35 6.40 6.49

Nitrobenzene conversion (%) 2.3 5.1 9.3 20.4 45.3 72.1

TF (aniline)c 5.6 6.3 7.5 8.3 9.2 9.8

Table 4 Recycling eciency of nitrobenzene reduction catalysis by CuCl2 2H2O immobilized on P(4-VP) in contact with 80% aqueous 2-ethoxyethanola Cycle no. 1 2 3
a

Yield of CO2b (mmol) 181.6 103.1 19.0

Yield of anilineb (mmol) 58.9 33.2 6.1

TF (aniline)c 9.8 5.5 1.0

0.5 g of P(4-VP), 8 mL of 2-ethoxyethanol, 2 mL of H2O, [Cu] = 2.0 104 mol, (2.5 wt%), 1.2 mL of nitrobenzene (8.1 103 mol), nitrobenzene/Cu = 44, P(CO) = 27.2 atm at 150 C. b Based on aniline formed after a given time. Selectivity 98%. c Turnover frequency (aniline) = ([(mol of aniline)/(mol of Cu) (rt)]) 24 h, where (rt) is the reaction time in hours. Experimental uncertainty ca. 15%.

0.5 g of P(4-VP), 8 mL of 2-ethoxyethanol, 2 mL of H2O, [Cu] = 2.0 104 mol, (2.5 wt%), 1.2 mL of nitrobenzene (8.1 103 mol), nitrobenzene/Cu = 44, P(CO) = 27.2 atm at 150 C. b Based on aniline formed after 72 h. Selectivity 98%. c Turnover frequency (aniline) = ([(mol of aniline)/(mol of Cu) (rt)]) 24 h, where (rt) is the reaction time in hours. Experimental uncertainty ca. 15%.

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4. Conclusions The following conclusions can be drawn from the characterization and catalytic studies of the WGSR and nitrobenzene reduction by CuCl2 2H2O immobilized on the aminated polymer P(4-VP) in contact with aqueous 2-ethoxyethanol under CO. The characterization study of the immobilized Cu solid by SEM, UVvis, EPR, FT-IR and XPS techniques shows the variation of the copper environment during the immobilization process. This study suggests that the nitrogen lone pair of the vinylpyridine of the P(4VP) coordinates to the copper metal center. Coordination crosslinks are also proposed which is consistent with the DSC data. The EPR studies of fresh and used catalyst show that there are two types of immobilized cupric polymer-complex: isolated complex and complexes bonded by dipoledipole interactions. The presence of terminal carbonyl in the used catalyst, indicated by the IR spectrum under WGSR conditions as well as the EPR and XPS studies, provides strong experimental evidence for the formation of Cu(I)CO/ P(4-VP) complexes as reaction intermediates. It was found that CuCl2 2H2O immobilized on P(4VP) in contact with aqueous 2-ethoxyethanol under CO formed a low active catalyst system for both the WGSR and the reduction of nitrobenzene to aniline and azobenzene. Acknowledgements The authors thank CONICIT-VENEZUELA (GC, S1-2435) and CDCH (PI: 03.17.5192.2003). We thank Reilly Industries INC for donating the poly(4-vinylpyridine) cross-linked polymer (lot no. 70515AA). Also, we squez, Facultad de Farmacia, Unithank Lic. Luis Va versidad Central de Venezuela, for the GCMS measurements and Lic. Juan Alvarez Facultad de Ciencias, Universidad Central de Venezuela, for TGA-DTA measurements. References
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