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 Citations (Scopus)

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 - Jan 1 1992

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Oligomerization
Rhodium
Carbon monoxide
Olefins
Hydrides
Ethylene
Alcohols
Carbonylation
Water gas shift
Butenes
Acetic acid
Propylene
Catalysts
Chemical analysis
Water

All Science Journal Classification (ASJC) codes

  • Engineering(all)

Cite this

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title = "Rhodium(I)-catalyzed alternating co-oligomerization of carbon monoxide with olefins: Synthetic and mechanistic studies",
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.",
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Rhodium(I)-catalyzed alternating co-oligomerization of carbon monoxide with olefins : Synthetic and mechanistic studies. / Sen, Ayusman; Brumbaugh, Jeffrey S.; Lin, Minren.

In: Journal of Molecular Catalysis, Vol. 73, No. 3, 01.01.1992, p. 297-323.

Research output: Contribution to journalArticle

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AU - Sen, Ayusman

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AB - 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.

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