Volume 67, 1971

Homogeneous catalysis by Pt(II)–Sn(II) chloride complex. Part 1.—Kinetics and mechanisms of the hydrogenations of acetylene and ethylene

Abstract

Detailed kinetics of the hydrogenation of acetylene and ethylene catalyzed by methanolic solutions of Pt(II)–Sn(II) chloride complexes have been studied within a temperature range 0 to 20°C and at pressures up to 100 Torr. Initial rates of hydrogenation exhibit maxima in terms of Sn to Pt atomic ratio or catalyst concentration, expressed by ν=kKhcPhcPh/(1 +KhcPhc) for fixed Sn/Pt = 10, where Ph and Phc are pressures of hydrogen and hydrocarbon respectively, and k and Khc are constants. Acetylene is consecutively hydrogenated to ethane via ethylene as an intermediate. In the reaction of C2H2 or C2H4 with D2 in CH3OH, hydrogen atoms in the hydrocarbon are hardly substituted with deuterium, and C2H4 or C2H6 is produced predominantly. Acetylene-d2 also hardly exchanges its D-atoms in the reaction with H2 in CH3OH and cis-C2H2D2 is formed preferentially, while the exchange proceeds to a considerable extent in the case of C2D4.

These results are interpreted in terms of heterolytic splitting of hydrogen, competitive coordination of acetylene and ethylene, and successive reactions with hydride and protonic hydrogens.

Article information

Article type
Paper

Trans. Faraday Soc., 1971,67, 3283-3296

Homogeneous catalysis by Pt(II)–Sn(II) chloride complex. Part 1.—Kinetics and mechanisms of the hydrogenations of acetylene and ethylene

I. Yasumori and K. Hirabayashi, Trans. Faraday Soc., 1971, 67, 3283 DOI: 10.1039/TF9716703283

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