Rhodium(I)-catalyzed alternating co-oligomerization of carbon monoxide with olefins: Synthetic and mechanistic studies

Ayusman Sen, Jeffrey S. Brumbaugh, Minren Lin

Research output: Contribution to journalArticle

24 Scopus citations

Abstract

Rhodium(I) phosphine complexes were found to catalyze the alternating co-oligomerization of ethylene and carbon monoxide in appropriate solvents. In a mixture of alcohol (ROH) and acetic acid, the products were H(CH2CH2CO)nCH2CH3 and H(CH2CH2CO)nOR (n= 1-4). Only the oligomeric polyketones were formed when a mixture of alcohol and water was used as the solvent. The effect of solvent composition and additives on the product distribution was studied extensively. The reactions were initiated by a rhodium-hydride species formed through the water-gas shift reaction. The chain growth involved the alternate insertions of ethylene and carbon monoxide into the initial rhodium-hydride bond. The oligomeric polyketoesters were formed by the alcoholysis of the intermediate rhodium-acyl species, whereas the oligomeric polyketones were generated through a bimolecular reductive elimination from the intermediate rhodium alkyls and a rhodium hydride. The catalyst system was also found to effect the carbonylation of propylene and butene.

Original languageEnglish (US)
Pages (from-to)297-323
Number of pages27
JournalJournal of Molecular Catalysis
Volume73
Issue number3
DOIs
StatePublished - Jun 1992

All Science Journal Classification (ASJC) codes

  • Engineering(all)

Fingerprint Dive into the research topics of 'Rhodium(I)-catalyzed alternating co-oligomerization of carbon monoxide with olefins: Synthetic and mechanistic studies'. Together they form a unique fingerprint.

  • Cite this