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NANO LETTERS

Dendritic Nanoreactors Encapsulating Pd Particles for Substrate-Specific Hydrogenation of Olefins


Masahiko Ooe, Makoto Murata, Tomoo Mizugaki, Kohki Ebitani, and Kiyotomi Kaneda*
Department of Chemical Science and Engineering, Graduate School of Engineering Science, Osaka UniVersity, 1-3 Machikaneyama, Toyonaka, Osaka 560-8531, Japan
Received June 26, 2002; Revised Manuscript Received July 15, 2002

2002 Vol. 2, No. 9 999-1002

ABSTRACT
Dendrimer-encapsulated Pd(0) nanoparticles inside poly(propylene imine) (PPI) dendrimers functionalized with triethoxybenzamide groups have been prepared by extraction of Pd2+ and subsequent chemical reduction. The resulting dendrimerPd nanocomposites are unique catalysts for substrate-specific hydrogenation of polar olefins, due to the strong interaction between polar substrates and tertiary amino groups within the dendrimers.

Dendrimers are novel and well-defined cascade macromolecules with monodispersed molecular weight and specific number of end groups.1,2 The unique architecture of dendrimers provides special opportunities for host-guest chemistry.3 Meijer et al. proposed the concept of the dendritic box in which organic dyes are encapsulated through electrostatic interactions.4 Recently, research groups of Crooks,5-8 Tomalia,9,10 and Esumi11 independently have reported preparation of transition metal nanoparticles such as Cu, Pt, Ag, Au, and Pd within the definite internal cavity of the dendrimers to prevent the agglomeration of the metal nanoparticles. For Pd nanoparticles, Crooks et al. examined the hydrogenation of allylic alcohols using hydroxylterminated poly(amido amine) (PAMAM) dendrimers whose congested surfaces act as nanoscopic filters for substrate molecules.7,8 To the best of our knowledge, however, the above catalytic performance using the dendrimer-encapsulated Pd nanoparticles was noted only for the substrate selectivity based on molecular size. In this paper, we report substrate-specific hydrogenation of olefins using the triethoxybenzamide-terminated poly(propylene imine) (PPI) dendrimers as nanoreactors encapsulating Pd particles. The polar environment inside the dendrimers contributes to the substrate specificity, and the effect of substrate size on the hydrogenation rate was also investigated. Third to fifth generation PPI dendrimers were selected to construct nanocapsules because of their compact molecular sizes and the high density of amino groups within their dendritic structures. Fourth and fifth generation PPI dendrimers were synthesized by repetitive reaction sequences
* Corresponding author. E-mail: kaneda@cheng.es.osaka-u.ac.jp 10.1021/nl0202105 CCC: $22.00 Published on Web 08/01/2002 2002 American Chemical Society

Figure 1. Structure of triethoxybenzamide-dendrimer (G5-TEBA).

from the third generation molecule.12 Treatment of the above PPI dendrimers with triethoxybenzoic acid chloride gave surface functionalized dendrimers, Gn-TEBA (n ) 3, 4, 5) (Figure 1).13 Pd nanoparticles were prepared within GnTEBA by the following sequence: a predetermined quantity of aqueous Pd2+ were extracted into the interior of Gn-TEBA to give preorganized Pd2+ inside Gn-TEBA (Pd2+/GnTEBA), which were reduced with KBH4 to yield Pd nanoparticles encapsulated within Gn-TEBA (Pd(0)/GnTEBA).14 The 1H NMR spectrum of Pd2+/G4-TEBA in chloroform showed that the signals of the R-methylene protons of amino groups were broadened. In 14N NMR spectra, broad signals of amino groups for G4-TEBA shifted from -348.5 ppm to -347.2 ppm after treatment with Pd2+, while the amide signal at -278.8 ppm remained unchanged.15,16 These results suggest that Pd ions are coordinated to the amino groups within the dendrimers. Incorporation of Pd ions into dendrimers was also confirmed by the color change of the liquid phases: when an aqueous solution containing 10 mol of Pd2+ ions was added to 0.72 mol of G4-TEBA in chloroform, a light brown color of aqueous Pd2+ solution com-

Table 1. Hydrogenation of Olefins Using Dendrimer-Encapsulated Pd Nanoparticlesa

Figure 2. High-resolution transmission electron microscopy image of Pd(0)/G5-TEBA nanocomposites. The average particle size and distribution of Pd particles were determined by counting 100 particles.

pletely disappeared and then shifted to the chloroform solution. Using a 30:1 molar ratio of Pd2+ to G4-TEBA, a pale yellow color remained in the aqueous phase. ICP measurement of the aqueous phase revealed that the number of extracted Pd ions per dendrimer was 24.17 The number of the extracted Pd2+ corresponds to the total number of N3 and N4 nitrogen atoms, where tertiary amino groups in nth shell were labeled as Nn (n ) 1-5) from the core to the nth shell as shown in Figure 1. The above phenomena were also observed in the case of G3- and G5-TEBA, respectively. Treatment of Pd2+/Gn-TEBA in chloroform with KBH4 gave homogeneous dark brown solutions. XPS spectra of Pd2+/Gn-TEBA showed two bands at 343.0 and 337.9 eV due to Pd 3d5/2 and 3d3/2, respectively.18 After reduction with KBH4, the above two bands shifted to 340.6 (Pd 3d5/2) and 335.3 eV (Pd 3d3/2), which provides evidence for the complete reduction of Pd2+ to Pd0 species. The TEM image of Pd(0)/G5-TEBA in Figure 2 reveals the formation of roughly spherical and nearly monodispersed Pd nanoparticles. For Pd(0)/G3-TEBA, Pd(0)/G4-TEBA, and Pd(0)/G5-TEBA, the Pd particle diameters were 2.6 ( 0.6, 2.4 ( 0.6, and 2.3 ( 0.4 nm, respectively, which are smaller than the diameters of G3-TEBA (3.9 nm), G4-TEBA (4.3 nm), and G5-TEBA (4.9 nm), respectively.19 All the above Pd(0) nanoparticles were so stable that no aggregates of Pd particles were observed for several months in solution. By comparing the size of the dendrimers with that of the Pd(0) nanoparticles, we think that the dendrimers, especially G5-TEBA, encapsulate the Pd(0) nanoparticles. Crooks et al. have also prepared Pd(0) nanoparticles of 2-3 nm diameter by chemical reduction of Pd2+ species within the perfluorinated polyether-derivatized PPI dendrimer.20 Catalytic performance of the Pd(0)/Gn-TEBA was examined in hydrogenation of various olefins as shown in Table 1.21 Hydrogenation rates decreased with increasing generation of dendrimers from G3 to G5. A conjugated diene of 1,3cyclooctadiene was selectively hydrogenated to cyclooctene in >99% yield, and its initial hydrogenation rates using Pd1000

a Reaction conditions: catalyst 5.0 mol of Pd, substrate 1.0 mmol, toluene 12.5 mL, H2 1 atm, 30 C. b After 15 min, the reaction mixture contained n-hexane, 1-hexene, 2-hexene, and 3-hexene.

(0)/G3-TEBA, Pd(0)/G4-TEBA, and Pd(0)/G5-TEBA were 5.4, 4.1, and 2.9, respectively (entry 1). In the case of Pd/C catalyst, cyclooctene was formed together with a 19% yield of cyclooctane as an overhydrogenation product at a complete consumption of 1,3-cyclooctadiene. High selectivity for the monoene has been also reported in the catalytic hydrogenation using PAMAM dendrimer-encapsulated Pd nanoparticles10 and poly(N-vinyl-2-pyrrolidone) stabilized Pd colloids.22 The ring size effect of substrates on the hydrogenation rates was remarkable in the case of Pd(0)/G5-TEBA. Initial rates for the hydrogenation of cyclic conjugated dienes decreased in the order of cyclopentadiene > 1,3-cyclohexadiene > 1,3-cyclooctadiene (entries 1-3). The substrate size effect was also observed for the hydrogenations of acrylates and allylic alcohols. The initial hydrogenation rates for methylacrylate and tert-butylacrylate using Pd(0)/G5-TEBA were 7.6 and 3.1 (entries 6 and 7), while 11.2 and 3.8 were obtained for allyl alcohol and 2-methyl-3-buten-2-ol, respectively (entries 9 and 10). Using Pd/C catalyst, however, the hydrogenation rates were not strongly affected by the substrate size. A similar ring size effect using Pd(0)/GnTEBA was also observed in our previous hydrogenation catalyzed by the polystyrene-bound Pd complex, where the active sites are buried within the polystyrene matrix.23 On the contrary, when the phosphinated dendrimer-bound Pd(II) complex catalyst having active species located on the periphery of the dendrimers was used, hydrogenation rates were not strongly dependent on the substrate size.24 Thus, it can be concluded that surface congestion of the dendrimers, especially for G5-TEBA, suppresses the penetration of large substrates into the encapsulated Pd nanoparticles. Notably, in the hydrogenation of an equimolar mixture of 3-cyclohexene-1-methanol and cyclohexene using Pd(0)/G5Nano Lett., Vol. 2, No. 9, 2002

Scheme 1. Competitive Hydrogenations of (a) 3-Cyclohexene-1-methanol and Cyclohexene (b) N-Methyl-3-cyclohexene-1-carboxamide and Cyclohexene Using Various Pd Catalystsa

Reaction conditions: 3-cyclohexene-1-methanol 0.5 mmol, cyclohexene 0.5 mmol, catalyst 5.0 mol of Pd, toluene 12.5 mL, H2 1 atm, 30 C. bReaction conditions: N-methyl-3-cyclohexene1-carboxamide 0.5 mmol, cyclohexene 0.5 mmol, catalyst 5.0 mol of Pd, toluene 12.5 mL, H2 1 atm, 30 C.

Figure 3. 1H NMR spectra of the R-methylene proton signals of the tertiary amino group for (a) G5-TEBA, (b) G5-TEBA with cyclohexene, (c) G5-TEBA with 3-cyclohexene-1-methanol.

TEBA, cyclohexanemethanol was obtained exclusively without formation of cyclohexane. However, the selectivity for cyclohexanemethanol decreased in the case of Pd(0)/G3TEBA; cyclohexane was obtained in 7% yield at a complete consumption of 3-cyclohexene-1-methanol. Use of Pd/C resulted in formation of 60% yield of cyclohexanemethanol together with cyclohexane in 10% yield. A similar substrate specificity for polar substrates was also obtained in a competitive hydrogenation between N-methyl-3-cyclohexene1-carboxamide and cyclohexene; an olefinic bond of the carboxamide was exclusively reduced to give N-methylcyclohexanecarboxamide without contamination of cyclohexane. These results are summarized in Scheme 1. To the best of our knowledge, this is the first example of substratespecific catalysis on dendrimer-metal nanocomposites reported to date. The manner of interaction between dendrimer and substrates was examined by NMR and FT-IR spectroscopy. Figure 3 shows the R-methylene proton signal of the tertiary amino groups in G5-TEBA. In the presence of 3-cyclohexene1-methanol, the R-methylene proton signal at 2.17 ppm shifted downfield to 2.20 ppm, while there was no change in the proton signals of G5-TEBA in cyclohexene. In IR spectra of 3-cyclohexene-1-methanol, the free hydroxyl band at 3621 cm-1 disappeared when G5-TEBA coexisted. These data clearly show that hydrogen bonding between the hydroxyl group of the substrate and the amino group exists within the dendrimers. Hydrogen bonding plays an important role in the preferential penetration of polar substrates into the dendrimers, which could lead to the above remarkable substrate specificity. We think complete encapsulation of Pd nanoparticles within the G5 dendrimer can promote substrate specificity for 3-cyclohexene-1-methanol and N-methyl-3cyclohexene-1-carboxamide. The lower selectivity observed
Nano Lett., Vol. 2, No. 9, 2002

for the polar substrates in the case of Pd(0)/G3-TEBA could be attributed to partly exposed Pd nanoparticles that bulged out from the polar nanoenvironment inside the dendrimers.25 In conclusion, dendrimer-encapsulated Pd nanoparticles of 2-3 nm diameter have been prepared by the preorganization of Pd2+ ions inside the dendrimers and subsequent reduction with KBH4. Hydrogen bonding between internal amino groups and substrates leads to substrate-specificity in the G5 dendrimer-encapsulated Pd nanoparticles. The dendrimers act not only as templates of Pd nanoparticles, but also as nanoreactors capable of molecular recognition. This type of multifunctional dendrimer catalyst can contribute to the development of tailor-made nanoreactors with high substrate selectivity as enzymes. Acknowledgment. This work is supported by a Grantin-Aid for Scientific Research from the Ministry of Education, Science, Sports, Culture and Technology of Japan (14750626). We thank Dr. Fumiaki Hironaka (mcAnac) for TEM measurement. Supporting Information Available: Synthetic procedures and characterization data of the triethoxybenzamide-terminated poly(propylene imine) (PPI) dendrimers. This material is available free of charge via the Internet at http:// pubs.acs.org. References
(1) Tomalia, D. A.; Baker, H.; Dewald, J. R.; Hall, M.; Kallos, G.; Martin, S.; Roeck, J.; Ryder, J.; Smith, P. Polym. J. 1985, 17, 117. (2) Frechet, J. M. J.; Tomalia, D. A., Eds.; Dendrimers and Other Dendritic Polymers, J. Wiley & Sons: New York, 2001. (3) Lehn, J.-M. Supramolecular Chemistry: Concepts and PerspectiVes, VCH: New York, 1995. (4) Jansen, J. F. G. A.; de Brabander-van den Berg, E. M. M.; Meijer, E. W. Science 1994, 266, 1226. (5) Zhao, M.; Crooks, R. M. J. Am. Chem. Soc. 1998, 120, 4877. 1001

(6) Zhao, M.; Crooks, R. M. Angew. Chem., Int. Ed. Engl. 1999, 38, 364. (7) Crooks, R. M.; Zhao, M.; Sun, L.; Chechik, V.; Yeung, L. K. Acc. Chem. Res. 2001, 34, 181. (8) Niu, Y.; Yeung, L. K.; Crooks, R. M. J. Am. Chem. Soc. 2001, 123, 6840. (9) Balogh, L.; Tomalia, D. A. J. Am. Chem. Soc. 1998, 120, 7355. (10) Balogh, L.; Swanson, D. R.; Tomalia, D. A.; Hagnauer, G. L.; McManus, A. T. Nano Lett. 2001, 1, 18. (11) Esumi, K.; Suzuki, A.; Aihara, N.; Usui, K.; Torigoe, K. Langmuir 1998, 14, 3157. (12) de Brabander-van den Berg, E. M. M.; Meijer, E. W. Angew. Chem., Int. Ed. Engl. 1993, 32, 1308. (13) Schenning, A. P. H. J.; Elissen-Romn, C.; Weener, J. W.; Baars, M. W. P. L.; van der Gaast, S. J.; Meijer, E. W. J. Am. Chem. Soc. 1998, 120, 8199. (14) Typical procedures for the preparation of Pd(0)/G3-TEBA are as follows. To a 3 mL chloroform solution of G3-TEBA (3.4 mg, 0.625 mol) was added 2.0 mL of aqueous Na2PdCl4 solution (5.0 mM) and stirred vigorously at room temperature for 1 h. After the aqueous phase was decanted, the resultant chloroform solution of Pd2+/G3TEBA was treated with KBH4 (0.20 mmol) and stirred at room temperature for 1 h. The obtained dark brown solution containing Pd(0) nanoparticles was washed with deionized water and evaporated to give a residue that could be redissolved completely in various solvents such as toluene and chloroform. (15) Gupta, R. R.; Lechner, M. D. Chemical shifts and coupling constants for Fluorine-19 and Nitrogen -15, Springer: Berlin, 1998.

(16) Kooper, G. J. M.; van Genderen, M. H. P.; Elissen-Roman, C.; Baars, M. W. P. L.; Meijer, E. W.; Borkovec, M. J. Am. Chem. Soc. 1997, 119, 6512. (17) An amount of Pd ions extracted with G3-TEBA in chloroform was calculated from the difference of the Pd concentration in aqueous phases between before and after the extraction. (18) The data on the binding energy values are based on C1s binding energy (286.4 eV). (19) The mean diameters of Gn-TEBA were estimated by using MOPAC calculations. (20) Yeung, L. K.; Crooks, R. M. Nano Lett. 2001, 1, 14. (21) Typical procedures for hydrogenation reactions. Pd(0)/G5-TEBA (5 mol of Pd) was placed in a sidearmed flask attached to a gas buret and a manometer. The system was evacuated and filled with H2, followed by addition of 12.5 mL of toluene and stirred for half an hour at 30 C. Hydrogen uptake was measured just after the addition of olefin (1 mmol). The yields of products were determined by GC using an internal standard method. (22) Hirai, H.; Chawanya, H.; Toshima, N. Macromol. Chem., Rapid Commun. 1981, 2, 99. (23) Terasawa, M.; Kaneda, K.; Imanaka, T.; Teranishi, S. J. Catal. 1978, 51, 406. (24) Mizugaki, T.; Ooe, M.; Ebitani, K.; Kaneda, K. J. Mol. Catal. A: Chem. 1999, 145, 329. (25) Large aggregates of Au and Pt were observed when low generation PPI dendrimers were used. See: Michels, J. J.; Huskens, J.; Reinhoudt, D. N. J. Chem. Soc., Perkin Trans. 2 2002, 102.

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