Rhodium(I) catalyzed cooligomerization of carbon monoxide with ethylene. direct evidence for a single mode of stepwise chain growth

Ayusman Sen, Jeffrey S. Brumbaugh

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Abstract

Rhodium(I) compounds such as HRh(CO)(PPh3)3 and ClRh(CO)(PPh3)2, when dissolved in a ROH/HOAc mixture (ROH = MeOH, EtOH), were found to catalyze the cooligomerization of C2H4 and CO to a mixture of H(CH2CH2CO)nOR and H(CH2CH2CO)nCH2CH3 (n = 1-4). This reaction was found to proceed through a single mode of chain growth involving alternate insertions of CO and C2H4 with concomitant alcoholysis and hydrogenolysis of the resulting metal acyls and metal alkyls respectively. The cooligomerization of C2H4 and CO was also observed when Me2CO/H2O or Me3COH/H2O was used as solvent, the exclusive products being the ketones, H(CH2CH2CO)nCH2CH3 (n = 1-4). No reaction was observed in the absence of H2O.

Original languageEnglish (US)
JournalJournal of Organometallic Chemistry
Volume279
Issue number1-2
DOIs
StatePublished - Jan 8 1985

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Rhodium
Carbon Monoxide
rhodium
Carbon monoxide
carbon monoxide
Ethylene
ethylene
hydrogenolysis
Hydrogenolysis
Growth
Metals
Ketones
ketones
metals
insertion
products

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

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title = "Rhodium(I) catalyzed cooligomerization of carbon monoxide with ethylene. direct evidence for a single mode of stepwise chain growth",
abstract = "Rhodium(I) compounds such as HRh(CO)(PPh3)3 and ClRh(CO)(PPh3)2, when dissolved in a ROH/HOAc mixture (ROH = MeOH, EtOH), were found to catalyze the cooligomerization of C2H4 and CO to a mixture of H(CH2CH2CO)nOR and H(CH2CH2CO)nCH2CH3 (n = 1-4). This reaction was found to proceed through a single mode of chain growth involving alternate insertions of CO and C2H4 with concomitant alcoholysis and hydrogenolysis of the resulting metal acyls and metal alkyls respectively. The cooligomerization of C2H4 and CO was also observed when Me2CO/H2O or Me3COH/H2O was used as solvent, the exclusive products being the ketones, H(CH2CH2CO)nCH2CH3 (n = 1-4). No reaction was observed in the absence of H2O.",
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T1 - Rhodium(I) catalyzed cooligomerization of carbon monoxide with ethylene. direct evidence for a single mode of stepwise chain growth

AU - Sen, Ayusman

AU - Brumbaugh, Jeffrey S.

PY - 1985/1/8

Y1 - 1985/1/8

N2 - Rhodium(I) compounds such as HRh(CO)(PPh3)3 and ClRh(CO)(PPh3)2, when dissolved in a ROH/HOAc mixture (ROH = MeOH, EtOH), were found to catalyze the cooligomerization of C2H4 and CO to a mixture of H(CH2CH2CO)nOR and H(CH2CH2CO)nCH2CH3 (n = 1-4). This reaction was found to proceed through a single mode of chain growth involving alternate insertions of CO and C2H4 with concomitant alcoholysis and hydrogenolysis of the resulting metal acyls and metal alkyls respectively. The cooligomerization of C2H4 and CO was also observed when Me2CO/H2O or Me3COH/H2O was used as solvent, the exclusive products being the ketones, H(CH2CH2CO)nCH2CH3 (n = 1-4). No reaction was observed in the absence of H2O.

AB - Rhodium(I) compounds such as HRh(CO)(PPh3)3 and ClRh(CO)(PPh3)2, when dissolved in a ROH/HOAc mixture (ROH = MeOH, EtOH), were found to catalyze the cooligomerization of C2H4 and CO to a mixture of H(CH2CH2CO)nOR and H(CH2CH2CO)nCH2CH3 (n = 1-4). This reaction was found to proceed through a single mode of chain growth involving alternate insertions of CO and C2H4 with concomitant alcoholysis and hydrogenolysis of the resulting metal acyls and metal alkyls respectively. The cooligomerization of C2H4 and CO was also observed when Me2CO/H2O or Me3COH/H2O was used as solvent, the exclusive products being the ketones, H(CH2CH2CO)nCH2CH3 (n = 1-4). No reaction was observed in the absence of H2O.

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