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versão impressa ISSN 0001-3765versão On-line ISSN 1678-2690

An. Acad. Bras. Ciênc. v.80 n.2 Rio de Janeiro jun. 2008 



Thermal properties of metal-metal bonded Pd(I) complexes supported onto porous Vycor glass



Iara F. GimenezI,II; Oswaldo L. AlvesI

ILQES - Laboratório de Química do Estado Sólido, Instituto de Química - UNICAMP, Caixa Postal 6154, 13084-971 Campinas, SP, Brasil
IIDepartamento de Química, CCET/UFS, Campus Universitário Prof. José Aloísio de Campos, Av. Marechal Rondon s/n, 49100-000, São Cristovão, SE, Brasil

Correspondence to




Thermal behavior of the complexes Pd2(dppm)2Cl2, Pd2(dppm)2(SnCl3)Cl and Pd2(dppm)2(SnCl3)2 (dppm = bis[diphenylphosphino(methane)], ((C6H5)2PCH2P(C6H5)2) in the solid state and immobilized onto porous Vycor glass was studied. Similar decomposition mechanisms were observed for the solid and immobilized complexes, with a small thermal stabilization upon immobilization. The decomposition products were characterized by X-ray diffractometry, Raman and diffuse reflectance infrared spectroscopy, which indicated the presence of a mixture of metallic palladium and oxidized species such as PdO,condensed phosphates, SnO2 and SnP2O7. According to X-ray diffractometry, the decomposition products of the immobilized complexes presented higher amounts of PdO than the solid-state residues, probably as an effect of interactions with silanol groups present in the glass surface.

Keywords: palladium(I) complex, porous Vycor glass, bis[diphenylphosphino(methane)], thermogravimetric analysis.


Estudos dos complexos Pd2(dppm)2Cl2, Pd2(dppm)(SnCl3)Cl e Pd2(dppm)2(SnCl3) (dppm = bis[diphenylphosphino(methane)], (C6H5)2PCH2P(C6H5)2) por análise termogravimétrica (TG), no estado sólido e imobilizados no vidro poroso Vycor, são descritos. Os mecanismos de decomposição dos complexos no estado sólido e imobilizados no vidro poroso Vycor são similares e apenas uma ligeira estabilização é observada mediante a imobilização. Os produtos de decomposição foram caracterizados por difração de raios-X, espectroscopias Raman e de Refletância difusa no infravermelho, indicando a presença de uma mistura de paládio metálico e espécies oxidadas tais como PdO, fosfatos condensados, SnO2 e SnP2O7. Os produtos de decomposição dos complexos imobilizados no PVG apresentaram quantidades mais elevadas de PdO do que os resíduos no estado sólido, segundo a difração de raios-X, em virtude provavelmente da ocorrência de reações com grupamentos da superfície do vidro, bem como pelo fato de que as moléculas adsorvidas se encontram isoladas umas em relação às outras.

Palavras-chave: complexos de paládio(I), vidro poroso Vycor, bis[difenilfosfino)metano, análise termogravimétrica.




The study of supported organometallics and transition metal complexes is motivated mainly by applications as catalysts (Ando et al. 2004, Kureshi et al. 2004) and molecular precursors to advanced materials such as gas sensors (Alves et al. 2005, Silva et al. 2006), semiconductors, and metallic particles (Sunil et al. 1993). In particular, heterogeneous catalysts containing Pd or Pt have been studied owing to their activity in oxidation of CO, hydrogenation, (Evrard et al. 2004) and electrochemical oxidations (Yang and McElwee-White 2004). A previous paper by Richmond and co-workers reported the preparation of dinuclear phosphine-bridged palladium(I) species and their silica-bound analogues as catalysts for the cyclization of aminoalkynes, showing that in some cases the catalytic activity is improved by the higher thermal stability of the supported catalyst (Richmondet al. 2002).

The family of complexes of interest here includes the complex containing metal-metal bonded Pt(I) atoms Pt2(dppm)2Cl2 (Glocking and Pollock 1972) and its palladium analogue, which can be used as homogeneous catalysts in several reactions (Kirss and Eisenberg 1989). The derivatives of SnCl2 insertion into Pd-Cl bonds of Pd2(dppm)2Cl2 also catalyze the alkoxycarbonylation of terminal alkenes (Nguyen et al. 2005). In this context, the thermal behavior of free and supported complexes is important both to evaluate the thermal stability and to identify decomposition products. However, for the complexes of interest here this aspect was still unexplored.

The interest in the reactivity of single bonded Pd2 moieties for sensor phases is a growing area and previous attempts to immobilize similar compounds onto polystyrene for application in separation of gases were unsuccessful due to steric demands (Lee et al. 1986). Recently we described the immobilization of Pd2(dppm)2Cl2, Pd2(dppm)2(SnCl3)Cl, and Pd2(dppm)2(SnCl3)2 onto porous Vycor glass (Gimenez and Alves 2002, 2004), which proved to be suitable precursors for gas sensing systems (Alves et al. 2005,Silva et al. 2006). We were further interested in studying the thermal stability of these immobilized species, since the gas insertions into the metal-metal bond can be reverted both by heating and inert-gas flow. In this paper we report the thermogravimetric study of the complexes Pd2(dppm)2Cl2, Pd2(dppm)2(SnCl3)Cl, and Pd2(dppm)2(SnCl3)2, both in the solid state and immobilized onto porous Vycor glass, as well as the characterization of the decomposition products by XRD, DRIFT, and Raman spectroscopy.




All the syntheses were carried out using solvents purified and dried by standard methods. PdCl2, dppm and anhydrous SnCl2 were purchased from Aldrich and used without further purification. The complexes Pd2(dppm)2Cl2 (1), Pd2(dppm)2(SnCl3)Cl (2) and Pd2(dppm)2(SnCl3)2 (3) were prepared by methods described in the literature (Balch and Benner 1982, Olmstead et al. 1979).


The complexes were immobilized onto 1-mm thick polished Vycor 7930 glass plates. Immobilization experiments were carried out by immersion of 10 ×10 × 1 mm glass plates into 1 10-3 mol L-1 methylene chloride solutions of the complex at room temperature for 24 hours. The solvent was removed under vacuum. The PVG-supported complexes will be referred in the text as

PVG/1 (PVG/Pd2(dppm)2Cl2),
PVG/2 (PVG/Pd2(dppm)2(SnCl3)Cl) and
PVG/3 (PVG/Pd2(dppm)2(SnCl3)2.


Thermogravimetric analyses were carried out in a TA Instruments 2960, using platinum sample holders, under the dynamic flow of dry synthetic air (20 mL min-1), at a heating rate of 10 K min-1.


All pyrolysis experiments of solid and immobilized complexes were carried out in platinum crucibles under air for 24 h at specified temperatures.


X-ray diffractograms were obtained with a Karl Zeiss URD-6, using Cu-ka radiation (l = 1.54060Å), with a step 2q 0.02/0.4 s.


Raman spectra were recorded on a Renishaw Raman Imaging Microscope System 3000, coupled to an optical microscope with resolution 1.5µm and a He-Ne (l = 632.8 nm) laser source. Sampling was accomplished by scanning different surface regions of the sample placed onto glass sheets.


Diffuse reflectance infrared spectra were obtained with a Nicolet 520 spectrophotometer in the spectral range 4000-400 cm-1 using KBr as reference.



Figure 1 shows the TG curves for the solid samples, while their corresponding data are displayed in Table I. The decomposition of 1 starts at 471 K with an abrupt mass loss up to 837 K corresponding to a 62% loss (calculated 62%), attributed to elimination of one P(Ph)2CH2Cl2 active radical and one dppm molecule. Formation of similar radical species was reported by Zayed and co-workers in the thermal decomposition of mononuclear Pt(dppm)Cl2 complexes in the range 393-773 K (Zayed et al. 1999). In the present case a further decomposition step can be observed above 837 K, with a mass loss of 13% attributed to the elimination of residual phosphine species and reduction of PdO eventually formed on the surface. The formation of metallic Pd residues or Pd/PdO mixtures rely on the pyrolysis conditions as well as on the presence of groups in the molecular structure able to generate reducing conditions during decomposition.





In the TG curve of compound 2, the mass gain starting from 474 K may be attributed to oxygen uptake. The mass increase at relatively low temperatures by oxygen absorption is commonly observed for Pd and Pt complexes such as [Pd(PPh3)4] and [Pt(PPh3)4], rendering species such as and Ph3PO (phosphinoxide) (Barbieri et al. 1995). As verified in Figure 1, the mass gain is followed by a gradual mass loss from 546 K to 968 K. No clear plateau can be defined but the curve derivative shows a broad feature from 546 to 822 K corresponding to a 49% loss. Probably the decomposition involves elimination of P(Ph)2CH2Cl2 plus one entire dppm (expected loss: 52%).

For compound 3 the initial 2% loss due to elimination of water suggests the presence of SnCl2 (hygroscopic) as an impurity. When this compound is put into CH2Cl2 solution the following chemical equilibrium takes place (Olmstead et al. 1979):

A large SnCl2 excess is necessary in the synthesis leading to the presence of SnCl2 as a product impurity. Exhaustive purification attempts by recrystallization will form compound 2 and, in fact these limitations precluded the crystal structure determination for this compound, since its earliest report (Olmstead et al. 1979). According to TG curve, compound 3 degrades with continuous mass loss from 413 K up to 916 K. In the range 586-683K the mass loss observed (24%) is coherent with loss of a P(Ph)2CH2Cl2 radical plus a Cl2 molecule (calculated 24%). The decomposition of the residue is gradative and incomplete with a final mass percent of 48%.

The decomposition products were characterized by XRD, DRIFT and Raman. According to X-ray diffraction, Figure 2, the main decomposition product of solid complex 1 is metallic palladium (2q = 40.1°, 46.6° and 68.1° (JCPDS)). For the complexes 2 and 3, residues contain SnO2 (2q = 26.5°, 34°, 38°, 51.8°) and Sn2PO7 (2q = 19.2°, 22.3°, 37.6°) in addition to metallic palladium.



DRIFT and micro-Raman spectroscopies suggested the presence of additional phases, mostly in the case of 1. For 1, the Raman spectrum (Fig. 3) shows the typical features of PdO (Chan and Bell 1984), probably not detected by X-ray diffraction due to its concentration on the surface. For compounds 2 and 3, SnO2 bands near 630 cm-1 dominate the Raman spectra (Fig. 3). For all samples, spectra of some surface regions show a pair of broad bands at 1330 cm-1 and 1580 cm-1 indicating amorphous carbon residues (Macedo et al. 2008). DRIFT spectrum of 1 (not shown) showed a broad band around 1000 cm-1 suggesting the presence of condensed phosphates. For 2 and 3, Sn2PO7 already detected by XRD was confirmed due to the bands at 1160 cm-1 and 1026 cm-1, assigned to nsym(P-O) and nasym(P-O) from terminal groups, respectively, and at 748 cm-1 assigned to nsym(P-O) from P-O-P bridges (Hubin and Tarte 1967, Guan et al. 2005). Also a strong band at 1280 cm-1 can be assigned to intra-chain PO moieties from condensed phosphates.



Thermal behavior of immobilized complexes was also studied. Figure 4 shows the TG curves of the PVG-supported complexes and for all samples the initial mass loss from 298 K to 423 K is due to elimination of adsorbed water from the glass surface. Up to 25% of PVG "dry mass" can be composed by adsorbed water as the pore surface is composed mainly by the very reactive silanol (Si-OH) groups (Hood and Nordberg 1938,1942). At higher temperatures all mass losses are attributed to decomposition of the complexes and from these curves as well as from the mass loss observed for solid samples, it is possible to estimate the amount of adsorbed complexes. The related data are displayed in Table II. The thermal decomposition of PVG/1 starts at 449 K with loss of 1%, followed by 1%. The initial decomposition temperature of the supported complex is slightly higher than in the solid state, indicating a stabilization of the supported complex. The thermal decomposition of PVG/2 starts at 510 K, with a deflection at 563 K and a gradual mass loss up to 919 K. Finally, for PVG/3 mass losses at 488 K, 573 K and 740 K can be observed, slightly higher than in the solid state.





As glass signals dominated the DRIFT and Raman spectra of PVG samples, only XRD was able to detect residues of the complexes. Interestingly in this case PdO peaks are observed in addition to metallic Pd for all samples, suggesting that the close contact of the complexes with silanol groups facilitates the formation of PdO, in contrast to the behavior of the solid complexes. For PVG/2 and PVG/3 the peaks of metallic palladium are weak in comparison to SnO2 and SnP2O7 peaks.

From the results of thermal analysis and characterization of the decomposition products, we conclude that the thermal stability of the complexes is improved by immobilization onto porous Vycor glass and the composition of the residues presents some differences. The decomposition mechanism is complex and involves concomitant processes such as elimination of P(Ph)2CH2Cl2 radicals and Cl2 molecules. The residues, both in the solid state and embedded in the glass, consist of a mixture of compounds such as oxides, phosphates and metallic palladium.



The authors are grateful to Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP, Brazil) for the financial support.



ALVES FL, RAIMUNDO JR IM, GIMENEZ IF AND ALVES OL. 2005. An organopalladium-PVC membrane for sulphur dioxide optical sensing. Sensors Actuators B 107: 47–52.         [ Links ]

ANDO R, YAGYU T AND MAEDA M. 2004. Characterization of oxovanadium (IV)-Schiff-base complexes and those bound on resin, and their use in sulfide oxidation. Inorg Chim Acta 357: 2237–2244.         [ Links ]

BALCH AL AND BENNER LS. 1982. Binuclear transition-metal complexes bridged by methylenebis(diphenylphosphine). Inorg Synth 21: 47–50.         [ Links ]

BARBIERI RS, BELLATO CR AND MASSABNI AC. 1995. Thermal-analysis of coordination-compounds.3. thermal decomposition of platinum complexes containing triphenylphosphine, triphenylarsine and triphenylstibine. Thermochim Acta 259: 277–286.         [ Links ]

CHAN SS AND BELL AT. 1984. Characterization of the preparation of Pd/SiO2 and Pd/La2O3 by laser Ramanspectroscopy. J Catal 89: 433–441.         [ Links ]

EVRARD D, GROISONK, MUGNIER Y AND HARVEY PD. 2004. The Pd4(dppm)4(H)22+ cluster: a precatalyst for the homogeneous hydrogenation of alkynes. Inorg Chem 43: 790–796.         [ Links ]

GIMENEZ IF AND ALVES OL.2002. Immobilisation of complexes containing metal-metal bonds in porous Vycorglass and subsequent insertion of gas molecules into the Pd-Pd bonds. Glass Technol 43C: 166–169.         [ Links ]

GIMENEZ IF AND ALVES OL. 2004. Properties of [Pd2X2(dppm)2] (X = Cl, SnCl3, dppm = bis(diphenylphosphino)methane) complexes on porous vycor glass. J Braz Chem Soc 15: 640–645.         [ Links ]

GLOCKING F AND POLLOCK RJI. 1972. Novel dimeric platinum( I) complex. J Chem Soc Chem Commun 88: 467– 467.         [ Links ]

GUAN X-H, LIU Q, CHEN GH AND SHANG C. 2005. Surface complexation of condensed phosphate to aluminum hydroxide: An ATR-FTIR spectroscopic investigation. J Colloid Interface Sci 289: 319–327.         [ Links ]

HOOD H AND NORDBERG ME. 1938. Treated borosilicate glass. US Patent 2,106,744.         [ Links ]

HOOD HP AND NORDBERG ME. 1942. Method of treating borosilicate glasses. US Patent 2,286,275.         [ Links ]

HUBIN R AND TARTE P. 1967. Spectre d’absorption infra-rouge des pyrophosphates et pyroarseniates cubiques d’éléments tetravalents X6P2O7 et X6As2O7. Spectrochim Acta 23A: 1815–1815.         [ Links ]

JCPDS – JOINT COMMITTEE ON POWDER DIFFRACTION STANDARDS FILES –International Centre for Diffraction Data.         [ Links ]

KIRSS RU AND EISENBERG R.1989. Di(phosphine)-bridged complexes of palladium – parahydrogen-induced polarization in hydrogenation reactions and structure determination of tris(µ-bis(diphenylphosphino)methane)dipalladium, Pd2(dppm)3. Inorg Chem 28: 3372–3378.         [ Links ]

KURESHY RI, KHAN NUH AND ABDI SHR. 2004. Dicationic chiral Mn(III) salen complex exchanged in the interlayers of montmorillonite clay: a heterogeneous enantioselective catalyst for epoxidation of nonfunctionalized alkenes. J Catal 221: 234–240.         [ Links ]

LEE C-L, YANG Y-P, RETTIG SJ, JAMES BR, NELSON DA AND LILGA MA. 1986. Synthesis and characterization of dinuclear palladium(I) and mononuclear palladium(II) complexes containing 1,1-bis(diphenylphosphino)ethane (dpmMe) and related mixed-ligand complexes containing dpmMe with either bis(diphenylphosphino)methane (dpm) or 2-(diphenylphosphino)pyridine (Ph2Ppy) – X-ray crystal-structures of PdCl2(dpmMe) and Pd2Cl2(µ-dpmMe)2. Organomet 5: 2220–2228.         [ Links ]

MACEDO JS, OTUBO L, FERREIRA OP, GIMENEZ IF, MAZALI IO AND BARRETO LS. 2008. Biomorphic activated porous carbons with complex microstructures from lignocellulosic residues, Microporous Mesoporous Mater 107: 276–285.         [ Links ]

NGUYEN DH, COPPEL Y, URRUTIGOITY M AND KALCK P. 2005. [Pd(H)(SnCl3)L2]: The key active species in the catalyzed alkoxycarbonylation reaction of terminal alkenes. J Organomet Chem 690: 2947–2951.         [ Links ]

OLMSTEAD MM, BENNER LS, HOPE H AND BALCH AL. 1979. Addition of tin(II) chloride to Pd2(Ph2PCH2PPh2)2Cl2 – Crystal and molecular-structure of Pd2(Ph2PCH2PPh2)2(SnCl3)Cl. Inorg Chim Acta 32: 193–198.         [ Links ]

RICHMOND MK, SCOTT SL, YAP GPA AND ALPER H. 2002. Preparation of dinuclear phosphine-bridged palladium(II) species and their silica-bound analogues as catalysts for the cyclization of aminoalkynes. Organomet 21: 3395–3400.         [ Links ]

SILVA KRB, RAIMUNDO JR IM, GIMENEZ IF AND ALVES OL. 2006. Optical sensor for sulphur dioxide determination in wines. J Agric Food Chem 54: 8697–8701.         [ Links ]

SUNIL D, SOKOLOV J, RAFAILOVICH MH, DUAN X AND GAFNEY HD. 1993. Evidence for the photodeposition of elemental iron in porous vycor glass. Inorg Chem 32: 4489–4490.         [ Links ]

YANG Y AND MCELWEE-WHITE L. 2004. Electrochemical oxidation of methanol using dppm-bridged Ru/Pd, Ru/Pt and Ru/Au catalyst. Dalton Trans 15: 2352–2356.         [ Links ]

ZAYED MA, ARIFIEN AESA AND HASSAN FSM. 1999. Investigation of complexes of diphenyl-phosphine derivatives by thermal and other physicochemical methods of analyses. J Thermal Anal 55: 205–212.         [ Links ]



Correspondence to:
Oswaldo L. Alves

Manuscript received on October 6, 2006; accepted for publication on October 23, 2007; contributed by OSWALDO L. ALVES*



* Member Academia Brasileira de Ciências

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