Open AccessMetal clusters in catalysis: Hydrocarbon reactions
Author(s) -
Kenneth G. Caulton,
M. G. Thomas,
Barrie Sosinsky,
E. L. Muetterties
Publication year - 1976
Publication title -
proceedings of the national academy of sciences of the united states of america
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.011
H-Index - 771
eISSN - 1091-6490
pISSN - 0027-8424
DOI - 10.1073/pnas.73.12.4274
Subject(s) - ruthenium , chemistry , catalysis , osmium , isomerization , cyclohexene , benzene , dehydrogenation , hydrocarbon , photochemistry , iridium , alkene , hexene , inorganic chemistry , organic chemistry , ethylene
A set of metal carbonyl clusters, Ru3 (CO)12 , Os3 (CO)12 , and Ir4 (CO)12 , has been evaluated as catalysts for a series of hydrocarbon reactions which comprise skeletal rearrangement, metathesis, dehydrogenation, hydrogenation, isomerization, and H-D exchange. None was especially effective as a hydrogenation catalyst even for olefins. Os3 (CO)12 was a catalyst for H-D exchange between C6 H6 and D2 at 195° but the ruthenium congener was inactive at temperatures below 175°, a temperature where ruthenium metal formed at an appreciable rate. Deuterium incorporation in the benzene was a single-step process. Ir4 (CO)12 was an effective catalyst for the conversion of cyclohexadiene to cyclohexene and benzene. A similar reaction occurred with cyclohexene but the rate was extremely low at 160°. The ruthenium and osmium clusters catalyzed the isomerization of linear hexenes, with the former the more active. Relative rates for the hexenes were 1 > 2 > 3. At high temperatures, the osmium and iridium clusters catalyzed skeletal reactions of 2-hexene, as evidenced by the formation of pentenes, heptenes, heptanes, and small amounts of propane.