Abstract
The hydrogenative ring opening of methylcyclobutane and methylcyclopentane was studied over silica-supported Pt and Pd catalysts by kinetic and infrared (IR) spectroscopic measurements. First, the temperature (473-673 K) and hydrogen pressure (3.3-73.2 kPa) dependences of the ring-opening reactions were determined. The reaction rates were determined over the initial and the working catalysts for both compounds. According to the type of product formation vs. hydrogen pressure dependence curves either dissociative or associative adsorption was suggested for methylcyclobutane and methylcyclopentane. The geometry of adsorbed intermediates was proposed on the basis of the regioselectivity of ring opening. The regioselectivity data show close to statistical ring opening for both compounds, which indicate flat-lying adsorbed intermediates. The structure of adsorbed intermediates was also studied by transmission IR spectroscopy. The H-D exchange reactions between the surface hydroxyl groups and adsorbed species in most cases confirmed the type of adsorption suggested by kinetic measurements.
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J.R. Anderson and M. Boudart, eds., Catalysis — Science and Technology, Vols. 1—8 (Akademie-Verlag, Berlin).
F.G. Gault, Adv. Catal. 30 (1981) 1.
Z. Paál and P. Tétényi, in: Specialist Periodical Reports on Catalysis, Vol. 5 (The Royal Society of Chemistry, London, 1982) p. 80; Z. Paál, Adv. Catal. 29 (1980) 273.
M. Bartök and ÁG. Zsigmond, in: Stereochemistry of Heterogeneous Metal Catalysis (Wiley, Chichester, 1985) p. 17.
Z. Paál, J. Mol. Catal. 94 (1994) 225.
A. da Costa Faro Jr. and C. Kemball, J. Chem. Soc. Faraday Trans. 91 (1995) 741.
M. Vaarkamp, P. Dijkstra, J. van Grondelle, J.T. Miller, F.S. Modica, D.C. Koningsberger and R.A. van Santen, J. Catal. 151 (1995) 330.
P.G. Smirniotis and E. Ruckenstein, Appl. Catal. A 123 (1995) 59.
G. Diaz, F. Garin, G. Maire, S. Alerasool and R.D. Gonzalez, Appl. Catal. A 124 (1995) 33.
G. Maire, G. Plouidy, J.C. Prudhomme and F.G. Gault, J. Catal. 4 (1965) 556.
L.H. Hilaire, G. Maire and F.G. Gault, Bull. Soc. Chim. France (1967) 886.
G. Maire and F.G. Gault, Bull. Soc. Chim. France (1967) 894.
B. Török, I. Pálinkö, Á. Molnár and M. Bartök, J. Catal. 143 (1993) 111; M. Bartök, B. Török, Á. Molnár and J. Apjok, React. Kinet. Catal. Lett. 49 (1993) 111.
B. Török and M. Bartök, Catal. Lett. 27 (1994) 281.
B. Török, I. Pálinkö and M. Bartök,Catal. Lett. 31 (1995) 421.
B. Török, I. Pálinkö, Á. Molnár and M. Bartök, J. Mol. Catal. 91 (1994) 61.
B. Török and Á. Molnár, J. Chem. Soc. Perkin Trans. I (1993) 801.
I. Pálinkö, F. Notheisz and M. Bartök, J. Mol. Catal. 63 (1990) 43.
G.V. Smith, M. Bartök, D. Ostgard and F. Notheisz, J. Catal. 101 (1986) 212.
M. Bartök, F. Notheisz, Á. G. Zsigmond and G.V. Smith, J. Catal. 100 (1986) 39.
B. Török, M. Török and M. Bartök, Catal. Lett. 33 (1995) 321.
G.A. Somorjai, Chemistry in Two Dimensions: Surfaces (Cornell University Press, Ithaca, 1981); in: Proc. 8th Int. Congr. on Catalysis, Berlin 1984, Vol. 1, p. 113 and references therein; A. Sárkány, J. Chem. Soc. Faraday Trans. 84 (1988) 2267; I. Pálinkö, F. Notheisz and M. Bartök, Catal. Lett. 1 (1988) 127.
W. Palczewska, Adv. Catal. 24 (1975) 245; in: Hydrogen Effects in Catalysis. Fundamentals and Practical Applications, eds. Z. Paál and P.G. Menon (Dekker, NewYork, 1988) ch. 14; R.H.E. Cardenas and D.E. Damiani, in: Catalysts Deactivation 1991, eds. C.H. Bartholomew and J.B. Butt (Elsevier, Amsterdam, 1991) p. 667.
I. Pálinkö, Á. Molnár, J.T. Kiss and M. Bartök, J. Catal. 121 (1990) 396.
I. Pálinkö, J.T. Kiss, F. Notheisz and M. Bartök, J. Mol. Catal. 77 (1992) 313.
F.Notheisz, I. Pálinkö and M. Bartök, Catal. Lett. 5 (1990) 229.
Z. Paál and P.G. Menon, eds., Hydrogen Effects in Catalysis (Dekker, NewYork, 1988).
R. Kramer and H. Zuegg, J. Catal. 85 (1984) 530.
R. Kramer and M. Fischbacher, J. Mol. Catal. 51 (1989) 247.
Z. Paál, J. Catal. 91 (1985) 181.
J.T. Kiss, I. Pálinkö and Á. Molnár, J. Mol. Struct. 293 (1993) 273.
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Török, B., Kiss, J. & Bartók, M. Characteristics of adsorbed intermediates in the hydrogenative ring opening of methylcyclobutane and methylcyclopentane over silica-supported Pt and Pd catalysts. Catalysis Letters 46, 169–179 (1997). https://doi.org/10.1023/A:1019026820387
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DOI: https://doi.org/10.1023/A:1019026820387