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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 , 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: firstname.lastname@example.org (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 . 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 .
Complex preparation A mixture of 0. This material will be referred herein as Cu/P(4-VP).5. we extend the use of the poly(4-vinylpyridine)/divinylbenzene(2%) polymeric matrix instead of pyridine as a ligand coordinated to CuCl2 salt. In a typical run. DSC. P(CO) = 1. 2.1.3%/4.0 · 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. EPR. Materials 2-Ethoxyethanol (Aldrich) was distilled from anhydrous stannous chloride.6%.8%/5. 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.1 eV for Cu.7 and 935. In the present study. The speciﬁed temperature was maintained at ±0. Infrared spectra were recorded on a Perkin–Elmer 1760X-FT spectrophotometer using KBr pellets for solid samples. Water was doubly distilled.5 °C by continuously stirring the oil bath as well as the reaction mixture which was provided with a Teﬂon-coated magnetic stirring bar. The amount of the absorbed copper on P(4-VP) was determined by subtracting the initial amount of copper salt from the unabsorbed one. Experimental 2.0 mL) were ana- 2.9 atm at 120 °C was observed for the more active 4-picoline (4-methylpyridine) system. The scanning electron micrographs were recorded on a Hitachi S-500 microscope with an energy dispersive X-ray detector.6 eV). it is important to follow the energy position of the LMM Auger line of Cu.8%/4. All gas mixtures He/H2 (91. and dried in vacuum at room temperature. The analyzed core-level lines were calibrated against the C 1s binding energy set at 285 eV of CHx neutral carbon. 933. v/v) and CO/ CH4/CO2/H2 (84. v/v).512 A. CuO and Cu(OH)2. UV–vis/DR.4%/8. Cu2O. the characterization by XPS. Nominal resolution was measured as full-width at half-maximum of 1.5 eV (survey spectrum). The reaction vessel was charged with a CO/CH4 mixture at the desired CO partial pressure (1. Nitrobenzene (Aldrich) was distilled in H2SO4 (1 M) and redistilled from CaCl2 prior to use.J. The solid was mounted on a standard sample stud. v/v. The column used was Carbosieve-B (80–100) mesh obtained from Hewlett–Packard using a He/H2 mixture as the carrier gas. v/v) were purchased from BOC Gases and were used as received. Gas samples analyses from catalytic runs were performed as described in detail previously  on a Hewlett–Packard 5890 Series II programmable (ChemStation) gas chromatograph ﬁtted with a thermal conductivity detector.4 atm at 25 °C. Pardey et al.1%/5. and then suspended in a circulating thermostated glycerol oil bath set at 110 °C for 8–48 h.0 · 10À4 mol).5 g of P(4-VP) and 0.8%. The thermal behavior studies were carried out using a TA Instruments SDT 2960 Simultaneous DTA-TGA analyzer.2%. 2. Glass transition temperatures were measured on a Perkin–Elmer DSC 7 at a rate of 20 °C/ min under a nitrogen purge. washed with 5 mL of 2-ethoxyethanol/H2O 8/2. 2. Since the Cu2p line is rather insensitive to the oxidation state of copper (the Cu 2p3/2 component is at: 932. CO/CH4 (95.2. / 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 . the loaded polymer beads and 10 mL of 80% aqueous 2-ethoxyethanol were added to the glass reactor vessel. but 1.0341 g (2. Dichlorocopper(II) salt (Merck) was used as received. then the solution was degassed by three freeze–pump–thaw cycles.3.6. The signals were deconvoluted using mixed Gaussian–Lorentzian curves where the Gaussian character was set at 80%. Photoelectron spectra of the solid were recorded with a VG-220i-XL ESCALAB spectrometer using monochromatized X-ray Mg Ka radiation (1235. 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.0 (core-level spectrum) to 1. TF(H2) of about 6 mol/ day for [Cu] = 20 mM (2. Poly(4-vinylpyridine)/divinylbenzene(2%) (P(4-VP)).4. For example. we report the preparation. 932.9 atm at 110 °C). respectively). using a rectangular cavity operating in the TE 102 mode. . The resulting blue polymer was ﬁltered. was used as provided by Reilly Industries. Gas samples (1. 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 . 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 . FT-IR. Here. Electron paramagnetic spectroscopy experiments were carried out in a conventional Varian E-line X-band spectrometer.
Magniﬁcation 5000·. Methane was used as internal standard to allow calculation of absolute quantities of CO consumed and H2 and CO2 produced during a time interval. . They observed the formation of tetrapyridine–Cu(II) complexes. the Parr reactor was charged with the CO/CH4 mixture (27. Results and discussion 3.5 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.2 atm partial CO pressure at 150 °C) and placed in the oil bath at 150 °C for 4–72 h. UV–vis/DR. This solution in contact with 0. and analyzing known mixtures checked their validities. In a typical run. H2.J. with calibration curves being prepared periodically for CO. Jeschke. allowing its Fig. 3. 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. electron-nuclear double resonance methods (ENDOR) and molecular modelling techniques. After charging the mixture formed by the Cu/P(4-VP) ([Cu] = 2. 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. the reactor cooled to room temperature and excess pressure was vented and products analyzed by GC and GC– MS. 0. 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 .2. 2-ethoxyethanol at room temperature leads to the gradual formation of a green–blue solution. the reaction was stopped. Pardey et al. CH4. XPS. Fig.2 mL (8. Subsequent to the addition of nitrobenzene. 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)). DTA-TGA and DSC techniques.0341 g. 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. G. and CO2. are discussed. characteristic of the mature catalyst system. the results of SEM/EDX.0 · 10À4 mol) in 10 mL of 80% aq. The solution above the light brown–green solid remains uncolored.  reported the characterization by EPR and UV–vis spectroscopies of the water-soluble CuCl2/ P(4-VP) system. On the other hand. In this section. 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. Scanning electron micrograph of the Cu/P(4-VP) fresh catalyst sample. The SEM with energy dispersive X-ray (EDX) technique was used for studying the morphology of the solid samples.A.5 wt%) blue solid and 10 mL of 80% of aqueous 2-ethoxyethanol with CO (1. After a given time.1 · 10À3 mol) sample of nitrobenzene were added to the reaction vessel. Also. Coordination of the nitrogen atom of the pyridine moiety to the Cu(II) center was proposed. then (over 1–5 min) to a yellow color and to a ﬁnal light brown–green color. the addition of 2% of divinylbenzene to the poly(4-vinlypyridine) polymer makes the latter insoluble in water and in all organic solvents. Characterization studies Kirsh et al. The P(4-VP) employed in their study was not cross-linked with any copolymer. respectively. FT-IR. EPR. 10 mL of 80% aqueous 2-ethoxyethanol and 1. 2. which were used to determine the nature of the water insoluble CuCl2/P(4-VP)/divinylbenzene(2%) immobilized species. from which it can be observed that the P(4-VP) is formed by agglomerates of grains with a smooth surface . Nitrobenzene reduction catalytic runs were conducted in a 150 mL mechanically stirred stainless steel Parr reactor. solubility in water. A response factor method for the GC analyses of the aniline was employed . We previously reported a SEM micrograph of a P(4-VP) sample. / Polyhedron 24 (2005) 511–519 513 lyzed by GC at the end of the reaction time. the blue solid ﬁrst changed to a light-blue color. 1.1.5 g of the Cu/P(4-VP) solid.
Similar EPR behavior was observed on reaction of CuCl2 Æ 2H2O (a) b g =2. 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. However. the amplitude of both spectra are the same. 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 ) was not observed. 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). The observed strong EPR signal in the used catalyst indicates the presence of copper(II) d9 species. However. the widening of the spectrum (a) is larger than spectrum (b). For example. 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- . In spite of the presence of the Cu(II) d9 species at high concentration in the light brown–green solid. one of the Cu(II) species is relatively easily reduced to Cu(I) and the other Cu(II) species remains unreduced.5 wt%) fresh catalyst (blue-colored solid) and these indicate the presence of copper(II) d9 paramagnetic species in this system as expected. and metalto-ligand charge transfer possible for d10 complex with aromatic structure also does not occur in the visible region of the spectrum . the amount of the fresh catalyst sample (blue solid) is roughly half that the used catalyst (light brown–green solid). EPR spectra in the 2500–3500 G region of: (a) Cu/P(4-VP) fresh catalyst.476 a g =2. EPR experiments show signals (Fig. 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. 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. 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). The samples of both did not have the same amounts of Cu/P(4-VP) as a result of handling procedures. Fig. whose morphology had not been modiﬁed.334 g = 2. did not show the presence of Cu and/or Cl. even though this solid was formed under CO/H2O mixture at the working temperature.514 A. 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. In spite of that. For that reason the intensity of spectrum (a) is smaller than the other spectrum.003 (b) ∆H = 100 Gauss Fig. Their EPR studies revealed changes in the form of the EPR spectrum upon increasing the copper concentration in the PE-gr-PAA matrix. Pardey et al. with 4-picoline and 2-picoline . 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). Under the CO/H2O mixture at the working temperature. The elemental analysis revealed Cu and Cl in the etched areas. 2.219 c g = 2 . 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 fact that the used catalyst has a light brown– green color suggested that Cu(II) is the predominant oxidation state. Pomogailo and Golubeva  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). both spectra are dissimilar due to diﬀerent molecular environments that surround the Cu(II) center in both solids.J. / Polyhedron 24 (2005) 511–519 2-ethoxyethanol after 72 h of stirring in air. a broad asymmetric singlet is observed which increases steadily in intensity as well as in width with increasing copper(II) content.106 d g = 2. (b) Cu/P(4-VP) used catalyst. 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. 2(a)) for the Cu/ P(4-VP) ([Cu] = 2. The same type of analysis of the smooth regions.
1449(m) and 1415(m. The atomic ratios IN/ICu = 2. broad) cmÀ1.3 529. The XPS spectrum of the fresh Cu/P(4-VP) catalyst shows Cu2p3/2 and CuLMM peaks at 933. The N1s spectrum for free P(4-VP) features a symmetric peak at 399.4.4. After charging the Cu/(P4-VP) blue solid with CO atmosphere (1.1 eV. but three of them (1596. 1451(m) and 1415(m. 1495(m). Two additional signals are observed.E. 400. 285. broad) cmÀ1. 532. the Cu2p3/2 component for the used Cu/P(4-VP) catalyst shows a sharp peak at 932. Unfortunately.1. and each peak can be deconvoluted into two peaks. respectively. which are assigned to Cu(II)–OH species .9 932.A. which leads to a competition for electronic density with the p-bonding molecular orbitals of the pyridine ring. Further. which constitutes an appropriate method for determining the copper valence will be explored in future investigations.9 eV (used catalyst) is attributed to carbon linked to the nitrogen atom of the pyridine heterocyclic . The O1s peak of the used catalyst is less intense than in the case of the fresh solid.9 (fresh catalyst) and 284. a XPS peak at 198. It is well known that Cu(I) complexes disproportionate rapidly at ambient temperature to Cu(II) and Cu(0) . the N1s peaks of the fresh and used catalysts are broader and more asymmetric than the one for free P(4-VP).. the FT-IR spectrum of fresh prepared KBr pellets of CuCl2/P(4-VP) ([Cu] = 2.6 Used catalyst 399. Also our EPR results include the existence of isolated Cu/P(4-VP) complexes (type-I complexes). +2 cmÀ1 in the mC–N and the side group absorption bands is observed.8 eV was observed. 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 fresh solid presents peaks at 529.5. broad) and side group absorption bands (C–C ring stretching vibrations) at 1554(m).8 569. .16. a comprehensive molecular explanation is not available.5 wt%) also shows the same bands. 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). 533.9 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. characteristic of the coordinated OH group. which could be assigned to Cu(II)–O species (e. at 532.1 198. 1493(m). and these results suggest the presence of Cu(I) as expected (vide supra). respectively. 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. within the detection limits of the XPS technique.5 eV and there is no sign of the shake-up features around 938–945 eV. However.4.3 eV.0 eV. +3 cmÀ1. of the considered photoelectron .0.0 eV. 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.0 and 533. / Polyhedron 24 (2005) 511–519 515 action between copper centers described by Pomogailo and Golubeva (type-II complexes).. 400.4 and 531. On the other hand. the copper concentration (2. Further. 530. 530. the XPS analysis showed O1s lines. Finally.6 eV. is attributed to the aliphatic carbons of adsorbed contaminants. The study of the magnetic susceptibility of this Cu/P(4-VP) system.5 wt%) used in our studies is not high enough to form clusters with strong exchange interactions (type-III complexes).1 eV. the blue solid changed to a light brown–green color characteristic of the mature catalyst system. Cu–OH).8 and 569. which is typical of metallic copper. On the other hand. 531. with one at 399. one with two and another with three N atoms bonded to the Cu. 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 .8 tion of the pyridine nitrogen of the P(4-VP) interacts with the copper cations. The value of 2. 531.0. 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. for both fresh and used catalyst. a peak at 567. Pardey et al. 284. 530.3 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. K.0 eV (Cl2p) reveals the presence of chloride that is coordinated to the copper in the fresh catalyst. Also. 1493 and 1449 cmÀ1) shifted by ca. The ﬁrst (the main peak) at 285.18].4.5 for the N/Cu ratio indicates that there are at least two diﬀerent Cu/P(4-VP) species.0. Two C1s intense peaks are present in the fresh and used catalyst. Table 1 shows the XPS data for the fresh (blue solid) and used (light brown–green solid) catalysts.3 529.1 285.4. However. a band at 3385 cmÀ1.9 933. is observed in both blue and light brown–green solid samples.0. The peak at 400.J.5 567. and the second peak at 285. which could be due to CO (coordinated to Cu) and to water.0. 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  anchored to the nitrogen-functionalized polymer. A slight blue shift of ca. However.0 285. in conjunction with intense shake-up features around 938–945 eV. Also.g.0 eV and the other at 400.
3. Pardey et al. Hence is it possible that the Cu bridges two diﬀerent polymer chains via coordination to the pyridine lone pair. FT-IR.6 °C after the immobilization of 2. hindered mobility of this nature provides a way for the enhancement in the Tg. The diﬀerential scanning calorimetry (DSC) technique was used to determine the glass transition temperatures. can displace one or two water molecules from CuCl2 Æ 2H2O and occupy the vacant coordination site on the Cu. It is noteworthy that the enhancing of the glass transition temperature of poly(4-vinylpyridine) after coordination to ruthenium  and osmium  complexes has been reported. Therefore. 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. The pyridine. the light brown–green colored solid contains Cu(II) and Cu(I) species. which is classiﬁed as a strong base. 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 DTA-TGA data (Fig. 3. .516 A. The poly(4-vinylpiridine)/2% cross-linked polymer. Tg increases by 23. / Polyhedron 24 (2005) 511–519 Further. Proposed Cu(II) structures in the fresh catalyst. propose the following structures (Scheme 1). The blue-colored solid contains Cu(II) species. Based on these spectroscopic results. we therefore.J. Fig. EPR. On the other hand. however a weight loss was observed around 100 °C due to the moisture content coming from the preparative method. 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. Proposed structures for Cu/P(4-VP) complexes The UV–vis.1 °C. 3) show that the Cu/P(4-VP) complex is stable at 250 °C.3. DTA-TGA curves for the Cu/P(4-VP) fresh catalyst sample. which exhibits a glass transition temperature (Tg) at 127.5 wt% of Cu(II) as the CuCl2 Æ 2H2O salt.
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.5 6. Applications of molecular modelling techniques for our water insoluble system are in progress and their results will be published in a forthcoming paper. / Polyhedron 24 (2005) 511–519 517 by the CO/H2O couple under the catalytic conditions.9 atm. and OHÀ ligands. selectivity and reproducibility typical of homogeneous catalysts with the easy product separation and catalyst recovery characteristic of heterogeneous catalysts [28–30].0 7.5 wt%). McCurdie and Belﬁore proposed the concept of coordination crosslinks for a metal acting as a bridge between pyridine ligands of two diﬀerent polymer chains . Quantitative analysis of gas samples taken after the reaction solution reached working temperature. c Turnover frequency (gas) = [(mol of gas)/(mol of Cu) · (rt)] · 24 h. which further by ligand exchange ´ reaction coordinates a CO molecule. under comparable reaction conditions. where (rt) is the reaction time in hours) are summarized in Table 2.9 7. two and three-coordination of a metal transition ion by coordinating P(4-VP) is well known [2. Cu(I)–CO/P(4-VP).2 CO2b (mol · 10À4) 4. respectively.5. 15%. 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 7.3 0 trimethylenedinitrilo-bis(2-butanone oximato)borate]). Also.8 6.3 TF(CO2)c 7.9 atm at 110 °C. b Based on the gas formed after a given time.6 10.2 7.2 TF(H2)c 6. Nitrobenzene reduction catalysis Immobilized transition metal complexes into polymers combine the good activity.1 10. 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).0 7.2 14. 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. where (rt) is the reaction time in hours.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) = 1.5 g of P(4-VP). The eﬀect of the reaction time on the WGSR catalytic activity was studied. 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) 4.2. yielding a yellow solid. 3. The immobilized carbonyl copper(I).4.25]. WGSR catalysis The copper immobilized complex ([Cu] = 2. which eventually through successive transformations leads to CO2 and H2 WGSR-products). The activities deﬁned as turnover frequency (turnover frequency (gas) = [(mol of gas)/(mol of Cu) · (rt)] · 24 h. Pardey et al. 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. The ligands coordinated to the Cu(II) d9 center of the blue-colored solid are ClÀ. Although. indicated that production of H2 and CO2 and consumption of CO follow the stoichiometry shown in Eq. Cu(LBF2)(CO).6 29. 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 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 . It is seen that the reaction time variation has no inﬂuence on the TF(H2) and TF(CO2) values. it must be subject to nucleophilic attack by water to generate a hydroxycarbonyl copper species. The structures (a) and (b) correspond to the blue solid. However. (1).0 28. P(CO) = 1. the last one coming from the hydrolysis of the pyridine residues of P(4-VP). Blank experiments revealed that no WGS reaction occurred in the absence of the catalyst. vinylpyridine and (OH)À.1 7.5 14. (2. [Cu] = 2.7 7.0 · 10À4 mol.J. Gagne et al. 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. 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). 2 mL of H2O. CO þ H2 O CO2 þ H2 3.0 a 0. 8 mL of 2-ethoxyethanol.  reported the reaction of carbon monoxide with blue Cu(LBF2) solution at 25 °C (LBF2 = [diﬂuoro-3. Accordingly. . species formed under the catalytic conditions plays an important role as a reaction intermediate in the catalytic cycle (namely. The last assignment is supported by the FT-IR and XPS results. Experimental uncertainty ca.6 6.A.
which are important parameters for the nitrobenzene reduction.23 7. b Based on aniline formed after a given time. c Turnover frequency (aniline) = ([(mol of aniline)/(mol of Cu) · (rt)]) · 24 h.1 · 10À3 mol). (2.35 6. under water gas shift reaction conditions. Experimental uncertainty ca.4 45. 1 2 3 a Yield of CO2b (mmol) 181.27 7. 2 mL of H2O. analyses of the eﬀects of varying the CO pressure.1 · 10À3 mol). P(CO) = 27. The results are in Table 4.26 mL of nitrobenzene.2 mL of nitrobenzene (8. 0. The calculated catalytic activity deﬁned as TF(aniline) was reproducible to ca. 8 mL of 2-ethoxyethanol.0 wt%.30 6.5 g of P(4-VP).5 wt%).1 TF (aniline)c 5.1 TF (aniline)c 9. Pardey et al. In addition.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. 1. Finally.3 5.65 mmol of aniline formed after 3 h (25% conversion)) was observed under the following reaction conditions: 0. control experiments show that no reaction was detected in the absence of the polymerimmobilized Cu complex. (2.2 mL of nitrobenzene (8. which eventually through successive transformations leads to aniline and azobenzene production).6 38. the concentration of Cu(I)–CO/P(4VP) species formed under the catalytic conditions is small as seen from the EPR studies described above.8 5.9 atm at 110 °C) previously employed in the catalysis of the WGSR above described.2 atm at 150 °C) summarized in Table 3.0 · 10À4 mol. but under the severe reaction conditions (P(CO) = 27. where (rt) is the reaction time in hours.1 9.40 6.0 Yield of anilineb (mmol) 58. 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. P(CO) = 27.9 4.1 19. Selectivity 98%. Reduction of nitrobenzene (1. 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 . are in progress and they will be reported elsewhere.2 mL) to aniline or other organic products  by this Cu/P(4-VP) ([Cu] = 2. hydrogen gas from the WGSR was not detected at the end of the reduction process.6. nitrobenzene/Cu = 44.2 atm at 150 °C. 2 mL of H2O.3 9. Cu(I)– CO/P(4-VP). [Cu] = 2. It is recognized that most Cu(I) complexes are air sensitive.6 6.49 Nitrobenzene conversion (%) 2.3 72. 15%.8 58.J.9 33. Experimental uncertainty ca. 15%.5 g of polymer. Recycling of the anchored catalyst The recycling eﬃciency of the CuCl2/P(4-VP) catalyst was studied in the reduction of nitrobenzene. 8 mL of 2-ethoxyethanol. 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) 1.3 7.5 1. / 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. 8 mL of 2-ethoxyethanol. species formed under the catalytic conditions plays an important role as reaction intermediate in the catalytic cycle (namely. 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). Selectivity 98%. A TF(aniline)/24 h value = 53 (0.2 9. The immobilized carbonyl copper(I). . 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 . c Turnover frequency (aniline) = ([(mol of aniline)/(mol of Cu) · (rt)]) · 24 h. Furthermore. Further. 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.5 g of P(4-VP). nitrobenzene/Cu = 44. Perhaps.2 atm at 150 °C. during the recycling process the system was contaminated with air even though care was taken to avoid that. 2 mL of H2O. Perhaps this is the reason for the low catalytic activity observed for both WGSR and nitrobenzene reduction.9 pH ﬁnal 7. [Rh] = 2. b Based on aniline formed after 72 h.2 7.5 16. The data obtained from these studies are reported in Table 3. Cu content and temperature on the activity of this Cu/P(4-VP) catalytic system.0 0. 1.0 · 10À4 mol. where (rt) is the reaction time in hours.5 wt%). 15% for a series of experimental runs.2 6.9 atm at 100 °C and [nitro- benzene]/[Rh] = 25 for the most active amine (2-picoline) system. Unfortunately.3 20. P(CO) = 0. [Cu] = 2.6 103.5 8.5 wt%) system in contact with 10 mL of 80% aqueous 2-ethoxyethanol were not observed under the mild reaction conditions (P(CO) = 1. 0. C6 H5 –NO2 þ 3CO þ H2 O ! C6 H5 –NH2 þ 3CO2 3. (2)) and additionally produces a minor amount of azobenzene (2%). The above results show that the polymer-anchored catalyst does not have high stability.518 A. A change of the catalytic activity was observed after a second use.
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