CHARACTERISTICS OF ADSORBED INTERMEDIATES IN THE HYDROGENATIVE RING-OPENING OF METHYLCYCLOBUTANE AND METHYLCYCLOPENTANE OVER SILICA-SUPPORTED PT AND PD CATALYSTS

The hydrogenative ring opening of methylcyclobutane and methylcyclopen tane was studied over silica-supported Pt and Pd catalysts by kinetic and infrared OR) spectroscopic measurements. First, the temperature (4 73-673 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. Accord ing 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 in termediates was proposed on the basis of the regioselectivity of ring opening. The regioselectivity data show close to statistical ring open ing for both compounds, which indicate flat-lying adsorbed intermediat es. The structure of adsorbed intermediates was also studied by transm ission 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.