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Polyhedron 24 (2005) 511–519 www.elsevier.


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 , Delfin Moronta e, Clementina Longo
b a ´ n, Escuela de Quı ´mica, Facultad de Ciencias, Universidad Central de Venezuela, Caracas, Venezuela Centro de Equilibrios en Solucio ´ lisis Petro ´ leo y Petroquı ´mica, Escuela de Quı ´mica, Facultad de Ciencias, Universidad Central de Venezuela, Caracas, Venezuela Centro de Cata c ´mica Organometa ´ lica y Macromolecular, Escuela de Quı ´mica, Facultad de Ciencias, Universidad Central de Venezuela, Centro de Quı Caracas, Venezuela d ´a Electro ´ nica, Facultad de Ciencias, Universidad Central de Venezuela, Caracas, Venezuela Centro de Microscopı e ´sica, Facultad de Ciencias, Universidad Central de Venezuela, Caracas, Venezuela Escuela de Fı 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), UV–vis/diffuse reflectance (UV–vis/DR), electron paramagnetic resonance (EPR), differential 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. Ó 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 modified by coordination to transition metal complexes [1,2]. The CuCl2 Æ 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 Ó 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.poly.2004.12.014

Cu–pyridine 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 filtration [10].

The amount of the absorbed copper on P(4-VP) was determined by subtracting the initial amount of copper salt from the unabsorbed one. 2.0341 g (2. 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. CuO and Cu(OH)2. Here. In the present study. Experimental 2.5 g of P(4-VP) and 0.J. This material will be referred herein as Cu/P(4-VP). The specified temperature was maintained at ±0. The analyzed core-level lines were calibrated against the C 1s binding energy set at 285 eV of CHx neutral carbon. and dried in vacuum at room temperature. Instrumentation The UV–vis spectra of the solutions (1 cm quartz cell) and of the solids (Labsphere RSA-PE-20 diffuse reflectance cell) were recorded on a Perkin–Elmer Lambda 10 spectrophotometer.8%/4. Water was doubly distilled.3. / Polyhedron 24 (2005) 511–519 We previously reported the homogenous catalysis of the WGSR by copper dichloride dissolved in aqueous substituted pyridine (methyl and dimethyl pyridines) solutions [11]. Infrared spectra were recorded on a Perkin–Elmer 1760X-FT spectrophotometer using KBr pellets for solid samples. Catalyst testing WGSR catalytic runs were conducted in all-glass reactor vessels consisting of a 100 mL round bottomed flask connected to an ‘‘O’’ ring sealed joint to a twoway Rotoflow Teflon stopcock attached to the vacuum line [4]. the loaded polymer beads and 10 mL of 80% aqueous 2-ethoxyethanol were added to the glass reactor vessel. UV–vis/DR.0 · 10À4 mol). respectively).8%/5. Nitrobenzene (Aldrich) was distilled in H2SO4 (1 M) and redistilled from CaCl2 prior to use. using a rectangular cavity operating in the TE 102 mode. 932.3%/4. Pardey et al.6 eV). Gas samples (1. Nominal resolution was measured as full-width at half-maximum of 1. Photoelectron spectra of the solid were recorded with a VG-220i-XL ESCALAB spectrometer using monochromatized X-ray Mg Ka radiation (1235. 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].5.0 mL) were ana- 2. washed with 5 mL of 2-ethoxyethanol/H2O 8/2. Dichlorocopper(II) salt (Merck) was used as received. v/v). was used as provided by Reilly Industries. EPR. All gas mixtures He/H2 (91.1. v/v) were purchased from BOC Gases and were used as received.6. The signals were deconvoluted using mixed Gaussian–Lorentzian curves where the Gaussian character was set at 80%.2%. The reaction vessel was charged with a CO/CH4 mixture at the desired CO partial pressure (1. 933. the characterization by XPS. v/v) and CO/ CH4/CO2/H2 (84. we extend the use of the poly(4-vinylpyridine)/divinylbenzene(2%) polymeric matrix instead of pyridine as a ligand coordinated to CuCl2 salt.7 and 935.9 atm at 110 °C).0 (core-level spectrum) to 1.9 atm at 120 °C was observed for the more active 4-picoline (4-methylpyridine) system. v/v.1 eV for Cu. DSC. it is important to follow the energy position of the LMM Auger line of Cu. In a typical run. 2.8%. The scanning electron micrographs were recorded on a Hitachi S-500 microscope with an energy dispersive X-ray detector.2. FT-IR. . Since the Cu2p line is rather insensitive to the oxidation state of copper (the Cu 2p3/2 component is at: 932.4. then the solution was degassed by three freeze–pump–thaw cycles. TF(H2) of about 6 mol/ day for [Cu] = 20 mM (2.5 °C by continuously stirring the oil bath as well as the reaction mixture which was provided with a Teflon-coated magnetic stirring bar.6%.4 atm at 25 °C. Poly(4-vinylpyridine)/divinylbenzene(2%) (P(4-VP)). Electron paramagnetic spectroscopy experiments were carried out in a conventional Varian E-line X-band spectrometer.1%/5.512 A. The resulting blue polymer was filtered. P(CO) = 1. Gas samples analyses from catalytic runs were performed as described in detail previously [4] on a Hewlett–Packard 5890 Series II programmable (ChemStation) gas chromatograph fitted with a thermal conductivity detector. The solid was mounted on a standard sample stud. Cu2O.5 eV (survey spectrum). For example. we report the preparation. Glass transition temperatures were measured on a Perkin–Elmer DSC 7 at a rate of 20 °C/ min under a nitrogen purge. The thermal behavior studies were carried out using a TA Instruments SDT 2960 Simultaneous DTA-TGA analyzer. 2.4%/8. and then suspended in a circulating thermostated glycerol oil bath set at 110 °C for 8–48 h.0 · 10À4 mol) of CuCl2 Æ 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 UV–vis spectrophotometry. The column used was Carbosieve-B (80–100) mesh obtained from Hewlett–Packard using a He/H2 mixture as the carrier gas. Complex preparation A mixture of 0. Materials 2-Ethoxyethanol (Aldrich) was distilled from anhydrous stannous chloride. but 1. CO/CH4 (95.

5 g of the Cu/P(4-VP) solid.1. then (over 1–5 min) to a yellow color and to a final light brown–green color.J.0 · 10À4 mol) in 10 mL of 80% aq. In a typical run. Magnification 5000·. which were used to determine the nature of the water insoluble CuCl2/P(4-VP)/divinylbenzene(2%) immobilized species. We previously reported a SEM micrograph of a P(4-VP) sample. This solution in contact with 0. and analyzing known mixtures checked their validities. 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]. respectively. and CO2.0341 g. The P(4-VP) employed in their study was not cross-linked with any copolymer. The SEM with energy dispersive X-ray (EDX) technique was used for studying the morphology of the solid samples. On the other hand. are discussed. allowing its Fig. the addition of 2% of divinylbenzene to the poly(4-vinlypyridine) polymer makes the latter insoluble in water and in all organic solvents. CH4. Scanning electron micrograph of the Cu/P(4-VP) fresh catalyst sample. [14] reported the characterization by EPR and UV–vis spectroscopies of the water-soluble CuCl2/ P(4-VP) system. the results of SEM/EDX. solubility in water. 2. Jeschke. Characterization studies Kirsh et al. 3. Subsequent to the addition of nitrobenzene. with calibration curves being prepared periodically for CO. 2-ethoxyethanol at room temperature leads to the gradual formation of a green–blue solution. . They observed the formation of tetrapyridine–Cu(II) complexes. characteristic of the mature catalyst system.2. the reactor cooled to room temperature and excess pressure was vented and products analyzed by GC and GC– MS. G. from which it can be observed that the P(4-VP) is formed by agglomerates of grains with a smooth surface [6]. After charging the mixture formed by the Cu/P(4-VP) ([Cu] = 2. Also.A. H2. Fig. / Polyhedron 24 (2005) 511–519 513 lyzed by GC at the end of the reaction time. electron-nuclear double resonance methods (ENDOR) and molecular modelling techniques. The solution above the light brown–green solid remains uncolored. General aspects Dissolution of a solid sample of CuCl2 Æ 2H2O (0.9 atm) and heating the reaction vessel and its content at 110 °C in a glycerol bath. The GC–MS 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. EPR. the blue solid first changed to a light-blue color. FT-IR. Pardey et al. Nitrobenzene reduction catalytic runs were conducted in a 150 mL mechanically stirred stainless steel Parr reactor. 10 mL of 80% aqueous 2-ethoxyethanol and 1. 1. Results and discussion 3. XPS. DTA-TGA and DSC techniques. Coordination of the nitrogen atom of the pyridine moiety to the Cu(II) center was proposed.2 mL (8. UV–vis/DR. A response factor method for the GC analyses of the aniline was employed [13]. Also the organic products were separated by column chromatography and analyzed by 13C and 1H NMR in a Jeol Eclipse 270 NMR spectrometer. [CuL4]2+ (L = a nitrogen atom of the P(4-VP)). In this section. the reaction was stopped. Methane was used as internal standard to allow calculation of absolute quantities of CO consumed and H2 and CO2 produced during a time interval.1 · 10À3 mol) sample of nitrobenzene were added to the reaction vessel. After a given time.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. 0.2 atm partial CO pressure at 150 °C) and placed in the oil bath at 150 °C for 4–72 h. 1 corresponds to the micrograph of the solid product of the reaction of P(4-VP) with the CuCl2 Æ 2H2O salt in contact with 80% aqueous 3.5 wt%) blue solid and 10 mL of 80% of aqueous 2-ethoxyethanol with CO (1. provided for this soluble copper (II) complex of poly(4-vinylpyridine) a model for the geometry of the first coordination sphere supported by a combination of EPR. the Parr reactor was charged with the CO/CH4 mixture (27.

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).514 A. even though this solid was formed under CO/H2O mixture at the working temperature. The UV–vis spectrum of CuCl2 Æ 2H2O dissolved in 80% aqueous 2-ethoxyethanol and the UV–vis/DR spectrum of the Cu/P(4-VP) blue solid sample show the displacement of the d–d transition band from 246 to 384 nm after the immobilization process. The observed modifications 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). (b) Cu/P(4-VP) used catalyst. 2(a)) for the Cu/ P(4-VP) ([Cu] = 2. The significant difference in the d–d transition bands between the solution and the solid would be a consequence of a different coordination environment around copper (II). a broad asymmetric singlet is observed which increases steadily in intensity as well as in width with increasing copper(II) content. In spite of that. whose morphology had not been modified. It has been stated that Cu(I) complexes would be colorless since d–d electronic transitions are not feasible to take place in a d10 system.476 a g =2. the fact that the used catalyst has a light brown– green color suggested that Cu(II) is the predominant oxidation state.003 (b) ∆H = 100 Gauss Fig. EPR experiments show signals (Fig. Fig. 2 also shows the EPR spectrum of the used catalyst (light brown–green colored solid) of the same system (b) in the presence of CO. / Polyhedron 24 (2005) 511–519 2-ethoxyethanol after 72 h of stirring in air. The observed strong EPR signal in the used catalyst indicates the presence of copper(II) d9 species. 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. the amount of the fresh catalyst sample (blue solid) is roughly half that the used catalyst (light brown–green solid). These data indicate the proximity of the structure of Cu(II) polymer-complexes and also suggests the existence of an increase in dipole–dipole interactions between them. did not show the presence of Cu and/or Cl.J.219 c g = 2 . Efforts to obtain the UV–vis/DR spectrum of the Cu/P(4-VP) light brown–green solid were unsuccessful inasmuch that this solid undergoes oxidation to produce the blue cupric polymer-complex during the handling procedures.106 d g = 2. However. both spectra are dissimilar due to different molecular environments that surround the Cu(II) center in both solids. Pardey et al. The samples of both did not have the same amounts of Cu/P(4-VP) as a result of handling procedures.334 g = 2. The observed narrowing in the width of the hyperfine 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- . The EPR result is similar to the one observed for the Cu/P(4-VP) (blue-colored solid) system mentioned above. 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. The elemental analysis revealed Cu and Cl in the etched areas. Similar EPR behavior was observed on reaction of CuCl2 Æ 2H2O (a) b g =2. 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 dipole–dipole interactions (type-II) and (3) clusters with strong exchange interactions (type-III). For example. the amplitude of both spectra are the same. Their EPR studies revealed changes in the form of the EPR spectrum upon increasing the copper concentration in the PE-gr-PAA matrix. In spite of the presence of the Cu(II) d9 species at high concentration in the light brown–green solid. and metalto-ligand charge transfer possible for d10 complex with aromatic structure also does not occur in the visible region of the spectrum [16]. However. Under the CO/H2O mixture at the working temperature. The same type of analysis of the smooth regions. with 4-picoline and 2-picoline [11].5 wt%) fresh catalyst (blue-colored solid) and these indicate the presence of copper(II) d9 paramagnetic species in this system as expected. For that reason the intensity of spectrum (a) is smaller than the other spectrum. the widening of the spectrum (a) is larger than spectrum (b). EPR spectra in the 2500–3500 G region of: (a) Cu/P(4-VP) fresh catalyst. 2.

the blue solid changed to a light brown–green color characteristic of the mature catalyst system.9 933. in conjunction with intense shake-up features around 938–945 eV. 1495(m). The O1s peak of the used catalyst is less intense than in the case of the fresh solid. +3 cmÀ1. broad) and side group absorption bands (C–C ring stretching vibrations) at 1554(m).. 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. broad) cmÀ1. 1493(m).0 eV. 530. 284. a peak at 567. a comprehensive molecular explanation is not available. and each peak can be deconvoluted into two peaks. and these results suggest the presence of Cu(I) as expected (vide supra).0 eV and the other at 400. However. The value of 2.4. The atomic ratios IN/ICu = 2. which could be due to CO (coordinated to Cu) and to water. one with two and another with three N atoms bonded to the Cu. 530.g.8 tion of the pyridine nitrogen of the P(4-VP) interacts with the copper cations.1 eV.0. Pardey et al.9 eV (used catalyst) is attributed to carbon linked to the nitrogen atom of the pyridine heterocyclic [19]. the XPS analysis showed O1s lines.5. However.9 (fresh catalyst) and 284. Two additional signals are observed.5 eV and there is no sign of the shake-up features around 938–945 eV. .0. respectively. the infrared spectrum of the light brown–green solid shows the mC–N band at 1598 cmÀ1 and the side group absorption bands (C–C ring stretching vibrations) at 1556(m).5 wt%) also shows the same bands. A slight blue shift of ca. 1449(m) and 1415(m. which are assigned to Cu(II)–OH species [20]. which is typical of metallic copper. is observed in both blue and light brown–green solid samples.0 eV (Cl2p) reveals the presence of chloride that is coordinated to the copper in the fresh catalyst.1. 285. of the considered photoelectron [23]. within the detection limits of the XPS technique. Also. with one at 399.A.J. K.1 285.3 eV indicates that a frac- Table 1 XPS data for fresh (blue-colored solid) and used (light brown–green colored solid) catalysts XPS peak Binding energy (eV) Fresh catalyst N1s O1s Cl2p C1s Cu2p3/2 CuLMM 399. Cu–OH). However. The FT-IR spectrum (KBr pellet) of a P(4-VP) sample shows one C–N ring stretching band (nC–N) at 1596(m. The first (the main peak) at 285. Two C1s intense peaks are present in the fresh and used catalyst. which could be assigned to Cu(II)–O species (e. The XPS spectrum of the fresh Cu/P(4-VP) catalyst shows Cu2p3/2 and CuLMM peaks at 933.0 285. Also. +2 cmÀ1 in the mC–N and the side group absorption bands is observed.0 and 533.1 eV. the copper concentration (2. 531. the Cu2p3/2 component for the used Cu/P(4-VP) catalyst shows a sharp peak at 932.9 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. Finally.4 and 531.3 529. 532. is attributed to the aliphatic carbons of adsorbed contaminants. Unfortunately.5 for the N/Cu ratio indicates that there are at least two different Cu/P(4-VP) species. broad) cmÀ1.4.0 eV. but three of them (1596. and the second peak at 285.4.4. After charging the Cu/(P4-VP) blue solid with CO atmosphere (1. which constitutes an appropriate method for determining the copper valence will be explored in future investigations.0..1 198. Further. 533.8 eV was observed. The FT-IR spectrum (KBr pellets) of the light brown–green color mature Cu/P(4-VP) catalyst sample shows one band in the mCO region at 2068 cmÀ1 (carbonyl-linear Cu species) suggesting the presence of a single carbonyl copper species [11] anchored to the nitrogen-functionalized polymer. The fresh solid presents peaks at 529. 400. Also our EPR results include the existence of isolated Cu/P(4-VP) complexes (type-I complexes). respectively.3 529. characteristic of the coordinated OH group. The study of the magnetic susceptibility of this Cu/P(4-VP) system. On the other hand.3 eV. at 532.8 and 569. IO/ICu = 1 and ICl/ ICu = 1 for the fresh catalyst were calculated from the XPS-peaks intensity ratios using the Scofield cross-section relative to each core level [22]. The slight blue shift observed in the nC–N of Cu/P(4-VP) could indicate N-coordination of the P(4-VP) polymer to the metal [2. On the other hand. the N1s peaks of the fresh and used catalysts are broader and more asymmetric than the one for free P(4-VP). 1493 and 1449 cmÀ1) shifted by ca.9 932. a band at 3385 cmÀ1.6 eV. Further. for both fresh and used catalyst.4. The N1s spectrum for free P(4-VP) features a symmetric peak at 399. 530.5 wt%) used in our studies is not high enough to form clusters with strong exchange interactions (type-III complexes).E.18]. 531.5 567.8 569. 1451(m) and 1415(m.0.16. which leads to a competition for electronic density with the p-bonding molecular orbitals of the pyridine ring.6 Used catalyst 399. The peak at 400.0. 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. Table 1 shows the XPS data for the fresh (blue solid) and used (light brown–green solid) catalysts. a XPS peak at 198. 400. It is well known that Cu(I) complexes disproportionate rapidly at ambient temperature to Cu(II) and Cu(0) [21]. the FT-IR spectrum of fresh prepared KBr pellets of CuCl2/P(4-VP) ([Cu] = 2. / Polyhedron 24 (2005) 511–519 515 action between copper centers described by Pomogailo and Golubeva (type-II complexes).

Tg increases by 23. 3. Pardey et al. DTA-TGA curves for the Cu/P(4-VP) fresh catalyst sample. The pyridine. which exhibits a glass transition temperature (Tg) at 127. Hence is it possible that the Cu bridges two different polymer chains via coordination to the pyridine lone pair. / Polyhedron 24 (2005) 511–519 Further. hindered mobility of this nature provides a way for the enhancement in the Tg.3. The blue-colored solid contains Cu(II) species. the light brown–green colored solid contains Cu(II) and Cu(I) species. Proposed structures for Cu/P(4-VP) complexes The UV–vis.1 °C.5 wt% of Cu(II) as the CuCl2 Æ 2H2O salt. propose the following structures (Scheme 1). can displace one or two water molecules from CuCl2 Æ 2H2O and occupy the vacant coordination site on the Cu. which is classified as a strong base. 3. forming coordination crosslinks as suggested by the XPS results. The Cu(I) species present in the used catalyst comes from the reduction of the Cu(II) (a) (b) N Cu N N N Cl Cu N OH Cl OH Scheme 1. EPR. Fig. Based on these spectroscopic results. Therefore. Proposed Cu(II) structures in the fresh catalyst. 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.6 °C after the immobilization of 2. The differential scanning calorimetry (DSC) technique was used to determine the glass transition temperatures. the DTA-TGA data (Fig. .516 A. On the other hand. we therefore. 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. however a weight loss was observed around 100 °C due to the moisture content coming from the preparative method.J. The poly(4-vinylpiridine)/2% cross-linked polymer. 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. 3) show that the Cu/P(4-VP) complex is stable at 250 °C.

7 7. Although. the last one coming from the hydrolysis of the pyridine residues of P(4-VP). Pardey et al. CO þ H2 O CO2 þ H2 3. . McCurdie and Belfiore proposed the concept of coordination crosslinks for a metal acting as a bridge between pyridine ligands of two different polymer chains [2].9 7. which eventually through successive transformations leads to CO2 and H2 WGSR-products). (2.25]. [Cu] = 2.9 atm at 110 °C. The immobilized carbonyl copper(I). The structures (a) and (b) correspond to the blue solid. species formed under the catalytic conditions plays an important role as a reaction intermediate in the catalytic cycle (namely. under comparable reaction conditions.1 10.9 atm. where (rt) is the reaction time in hours) are summarized in Table 2.2 14. 3.3 TF(CO2)c 7.5 6.5 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. which further by ligand exchange ´ reaction coordinates a CO molecule. Quantitative analysis of gas samples taken after the reaction solution reached working temperature.2 7.4. two and three-coordination of a metal transition ion by coordinating P(4-VP) is well known [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.6 10.5 wt%).2 CO2b (mol · 10À4) 4. The ligands coordinated to the Cu(II) d9 center of the blue-colored solid are ClÀ. 8 mL of 2-ethoxyethanol. Experimental uncertainty ca. Applications of molecular modelling techniques for our water insoluble system are in progress and their results will be published in a forthcoming paper. where (rt) is the reaction time in hours. / Polyhedron 24 (2005) 511–519 517 by the CO/H2O couple under the catalytic conditions.6 6. it must be subject to nucleophilic attack by water to generate a hydroxycarbonyl copper species. Cu(I)–CO/P(4-VP). (1). 2 mL of H2O. selectivity and reproducibility typical of homogeneous catalysts with the easy product separation and catalyst recovery characteristic of heterogeneous catalysts [28–30].A. However. Also. It is seen that the reaction time variation has no influence on the TF(H2) and TF(CO2) values. Accordingly.3 0 trimethylenedinitrilo-bis(2-butanone oximato)borate]).0 · 10À4 mol. The number of vinylpyridine groups coordinated to Cu(II) and Cu(I) species in the light brown–green colored solid is not known although the Cu(II) and Cu(I) species present in this solid must contain OHÀ and CO.1 7. ð 1Þ Table 2 WGSR by CuCl2 Æ 2H2O immobilized on P(4-VP) in contact with 80% aqueous 2-ethoxyethanola Reaction time (h) 8 12 18 24 48 H2b (mol · 10À4) 4.J.1 7. the similarity in the value of the mCO band (2068 cmÀ1) 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 ClÀ ligand by a CO molecule yielding a five coordinated [P(4-VP)x–Cu(OH)(CO)] (x = 3) immobilized species with three vinylpyridine groups (x) bonded to the Cu(I).2 TF(H2)c 6. and OHÀ ligands. 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 effect of the reaction time on the WGSR catalytic activity was studied. respectively. indicated that production of H2 and CO2 and consumption of CO follow the stoichiometry shown in Eq. yielding a yellow solid. The last assignment is supported by the FT-IR and XPS results.8 6.0 28. The activities defined as turnover frequency (turnover frequency (gas) = [(mol of gas)/(mol of Cu) · (rt)] · 24 h. vinylpyridine and (OH)À.6 29. 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.2. 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).5 g of P(4-VP). Cu(LBF2)(CO). Nitrobenzene reduction catalysis Immobilized transition metal complexes into polymers combine the good activity. Gagne et al. c Turnover frequency (gas) = [(mol of gas)/(mol of Cu) · (rt)] · 24 h.5 14. [26] reported the reaction of carbon monoxide with blue Cu(LBF2) solution at 25 °C (LBF2 = [difluoro-3. 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.0 7. Blank experiments revealed that no WGS reaction occurred in the absence of the catalyst. 15%.0 7.0 a 0. The structures (a) and (b) that we proposed for this water insoluble Cu(II)/P(4-VP) system are different from the one proposed for the water soluble copper(II) complex of poly(4-vinypyridine) described at the beginning of Section 3. WGSR catalysis The copper immobilized complex ([Cu] = 2. The IR and the X ray structure of this yellow solid show a mCO band at 2068 cmÀ1 and a single monocarbonyl copper(I) with a 20-electron count for the metal atom coordinated to five two-electron donors. P(CO) = 1.5. b Based on the gas formed after a given time.

nitrobenzene/Cu = 44. A TF(aniline)/24 h value = 53 (0. Further.9 atm at 110 °C) previously employed in the catalysis of the WGSR above described.0 0.5 g of polymer. .9 atm at 100 °C and [nitro- benzene]/[Rh] = 25 for the most active amine (2-picoline) system.5 wt%). where (rt) is the reaction time in hours.2 6. 0. [Cu] = 2. A change of the catalytic activity was observed after a second use. (2.5 g of P(4-VP). 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].6. The data obtained from these studies are reported in Table 3.1 19.2 atm at 150 °C.2 mL of nitrobenzene (8. Experimental uncertainty ca.3 7.5 g of P(4-VP).0 · 10À4 mol. The immobilized carbonyl copper(I). nitrobenzene/Cu = 44.J.6 103.518 A. a cycloaddition of the nitro group to the Cu–CO bond followed by elimination of CO2 should lead to the formation of the copper nitrosobenzene [Cu(g2–ONR)]+ species. In addition. 15% for a series of experimental runs.2 atm at 150 °C. 1 2 3 a Yield of CO2b (mmol) 181.8 5. which eventually through successive transformations leads to aniline and azobenzene production). Selectivity 98%.2 mL) to aniline or other organic products [31] by this Cu/P(4-VP) ([Cu] = 2.3 72. Experimental uncertainty ca. are in progress and they will be reported elsewhere.9 33. Recycling of the anchored catalyst The recycling efficiency of the CuCl2/P(4-VP) catalyst was studied in the reduction of nitrobenzene. P(CO) = 27. C6 H5 –NO2 þ 3CO þ H2 O ! C6 H5 –NH2 þ 3CO2 3. hydrogen gas from the WGSR was not detected at the end of the reduction process. The results are in Table 4. 8 mL of 2-ethoxyethanol. Perhaps. [Rh] = 2.0 · 10À4 mol. the concentration of Cu(I)–CO/P(4VP) species formed under the catalytic conditions is small as seen from the EPR studies described above. control experiments show that no reaction was detected in the absence of the polymerimmobilized Cu complex.5 wt%). Pardey et al. during the recycling process the system was contaminated with air even though care was taken to avoid that. Reduction of nitrobenzene (1.0 Yield of anilineb (mmol) 58.3 5. 1.3 9. P(CO) = 0.30 6. b Based on aniline formed after 72 h. analyses of the effects of varying the CO pressure. Cu content and temperature on the activity of this Cu/P(4-VP) catalytic system.6 38. ð 2Þ Table 3 Nitrobenzene reduction by CuCl2 Æ 2H2O immobilized on P(4-VP) in aqueous 2-ethoxyethanola Reaction time (h) 4 8 12 18 24 72 a Anilineb (mol · 10À4) 1.1 9.0 wt%.40 6.2 mL of nitrobenzene (8.1 · 10À3 mol).2 9. 0.9 pH final 7. but under the severe reaction conditions (P(CO) = 27. Selectivity 98%.6 6. Finally. 2 mL of H2O. where (rt) is the reaction time in hours. Furthermore. The above results show that the polymer-anchored catalyst does not have high stability. 8 mL of 2-ethoxyethanol. P(CO) = 27. which are important parameters for the nitrobenzene reduction.5 8. 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 turnover frequencies for aniline production were calculated as mol of aniline per mol of CuCl2 Æ 2H2O in 24 h (TF(aniline) = [(mol of aniline)/(mol of Cu) · (rt)] · 24 h). species formed under the catalytic conditions plays an important role as reaction intermediate in the catalytic cycle (namely. 15%. b Based on aniline formed after a given time.8 58. 1.26 mL of nitrobenzene. c Turnover frequency (aniline) = ([(mol of aniline)/(mol of Cu) · (rt)]) · 24 h. (2)) and additionally produces a minor amount of azobenzene (2%). / Polyhedron 24 (2005) 511–519 CuCl2 Æ 2H2O immobilized on P(4-VP) in contact with 80% aqueous 2-ethoxyethanol mainly catalyzes the reduction of nitrobenzene to aniline (98%) (Eq.49 Nitrobenzene conversion (%) 2.1 · 10À3 mol).5 1.27 7. 15%.9 4.5 16. c Turnover frequency (aniline) = ([(mol of aniline)/(mol of Cu) · (rt)]) · 24 h.5 wt%) system in contact with 10 mL of 80% aqueous 2-ethoxyethanol were not observed under the mild reaction conditions (P(CO) = 1. 2 mL of H2O. (2.2 atm at 150 °C) summarized in Table 3.1 TF (aniline)c 9. Cu(I)– CO/P(4-VP). Perhaps this is the reason for the low catalytic activity observed for both WGSR and nitrobenzene reduction. It is seen that the reaction time variation has a slight influence on the TF(aniline) values and that change can be associated with the slight shift to the basic zone on the pH final value of the catalytic mixture due to the increase of the amount of the aniline product (Brønsted base) with time.35 6.8 Table 4 Recycling efficiency of nitrobenzene reduction catalysis by CuCl2 Æ 2H2O immobilized on P(4-VP) in contact with 80% aqueous 2-ethoxyethanola Cycle no.4 45.2 7.23 7. 2 mL of H2O. It is recognized that most Cu(I) complexes are air sensitive.3 20.65 mmol of aniline formed after 3 h (25% conversion)) was observed under the following reaction conditions: 0. [Cu] = 2. 8 mL of 2-ethoxyethanol. Unfortunately.1 TF (aniline)c 5. under water gas shift reaction conditions. The calculated catalytic activity defined as TF(aniline) was reproducible to ca.

Berlin.J. Kirsh. J.B. Makromol. Soc. 801.T.W. P. Ebel. Rivas. Leon. Baricelli. Lujano. Ciardelli. Spinelli. Lett. V. Surf. for TGA-DTA measurements. Forster. Moronta. 48 (2003) 57. M. P. Canestrari. Wiley.L. Koval. [11] M.1). V. [22] J. Ferna V. Urbina. J. Kinet. Ortega. 15 (2004) 818. ´ . [16] C. Scofield. J. Catal. Chem. Clear. F. Cotton. A.A. 1997. Ortega. Eur. Relat. Universidad Central de Venezuela.C. Longo.J. Pardey. J.17. Getman. Wilson. P. Chem. Phenom. 9 (1971) 234. Gall. Bol. Hagerty. P. J. M. References [1] [2] [3] [4] M. C. Baricelli. p.M. Baricelli. Pardey. J. Advanced Inorganic Chemistry. E. A.G. 67 (1999) 325. [5] A. Baricelli. E. Lett. Pomogailo. p. Vos. Nakamoto. Moronta. New York. 1997 (Chapter 8). Jiang. McNair. C. M. S. 11 (2001) 67. T. Electron. Zamaraev.D. C.J. [10] D. Macromolecules 23 (1990) 4372. Catal. W.C. F. Mol. Longo. [27] A. Moya. The characterization study of the immobilized Cu solid by SEM.5192. UV–vis.A. 45 (2000) 347. Alvarez. p.A.A.a. 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It was found that CuCl2 Æ 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. indicated by the IR spectrum under WGSR conditions as well as the EPR and XPS studies. Interface Anal. P. McCurdie. 10 (1974) 671. / Polyhedron 24 (2005) 511–519 519 4.). D. Facultad de Farmacia. Catal. Pardey et al.A. M. Chem. [20] Z. 30 (1993) 445. Leon. Lujano. Soc.J.J. Wood. Macromolecular-metal Complexes. D. Electron. EPR. Z. G.D. VCH.A. A. React. C. English ed. J. H. Nomura. Lo S. J. [18] K. M. V. Wiley– Interscience. [6] A. J. Juan Alvarez Facultad de Ciencias. [14] Y. Longo. Delhalle. Catal. Pakkanen. M.D.J. for the GC–MS measurements and Lic. Spectrosc. T. C.A. P. Polymer 40 (1999) 2889. Polym. Schmidt.F. A.2003). L.J. Urbina. J. [30] A. J. Haukka.). Chernyak. 1996 (Chapter 2. Lujano.G. J. J. Chil. Lujano. Ferna Canestrari. S. Chil. Kovner. Sartori.A. D. P. Rivas. in: F. This study suggests that the nitrogen lone pair of the vinylpyridine of the P(4VP) coordinates to the copper metal center. ´ ndez. J.M. V. Polym. Kokorin. Belfiore. New York. Clark. M. Phenom. M.M. J. Gagne Soc. ´ ndez. C. [26] R. C. J. J. Pardey. Longo.M. Pardey. Bertolino. S. Yan ˜ ez. B. Organometal. Chem. J. [23] E. Lett. Inorg. Kelly. Krocza. 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 dipole–dipole interactions. Quı 46 (2001) 121. Chem. Allison. provides strong experimental evidence for the formation of Cu(I)–CO/ P(4-VP) complexes as reaction intermediates. D. Luis Va versidad Central de Venezuela. [21] F. [25] J. [31] K.A. B 104 (2000) 8382. Ferna Lujano. Pardey. Nunes-Pires. C. M. Laffineur. Polym. J. 99 (1977) 7170.J. ´m. Golubeva. R. Infrared and Raman Spectra of Organic and Coordination Compounds. A. 70515AA). M. [24] R. A 130 (1998) 1. Soc. 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