Cobalt-Mediated Phosphorus-Aryl Bond Cleavage during Hydroformylatlon

Robert A. Dubois, Philip E. Garrou, Karen D. Lavln, Harry R. Allcock

Research output: Contribution to journalArticle

46 Citations (Scopus)

Abstract

Close examination of 1-hexene hydroformylation reactions catalyzed by cobalt carbonyl/triarylphosphine(PPh3 or P(p-MeC6H4)3, linked to PPh2-functionalized polystyrene or PPh2-functionalized (aryloxy) phosphazenes) has revealed a time-dependent decrease in catalytic activity due to a cobalt-mediated phosphorus-carbon bond cleavage. Benzene and benzyl alcohol were detected as the cleavage products. When olefin is omitted from the reaction, R2PH is formed. The detection of p-MeC6H4CH2OH indicates that oxidative addition of the P-aryl bond to Co is at least a partial contribution to the process. These results are relevant to transition-metal-triarylphosphine catalysis in general and put a new perspective on “immobilized” homogeneous catalysis.

Original languageEnglish (US)
Pages (from-to)649-650
Number of pages2
JournalOrganometallics
Volume3
Issue number4
DOIs
StatePublished - Jan 1 1984

Fingerprint

Cobalt
Phosphorus
Catalysis
catalysis
phosphorus
cleavage
cobalt
Benzyl Alcohol
Hydroformylation
hexenes
Polystyrenes
Alkenes
Benzene
alkenes
Transition metals
catalytic activity
Catalyst activity
polystyrene
alcohols
Carbon

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

Dubois, Robert A. ; Garrou, Philip E. ; Lavln, Karen D. ; Allcock, Harry R. / Cobalt-Mediated Phosphorus-Aryl Bond Cleavage during Hydroformylatlon. In: Organometallics. 1984 ; Vol. 3, No. 4. pp. 649-650.
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Cobalt-Mediated Phosphorus-Aryl Bond Cleavage during Hydroformylatlon. / Dubois, Robert A.; Garrou, Philip E.; Lavln, Karen D.; Allcock, Harry R.

In: Organometallics, Vol. 3, No. 4, 01.01.1984, p. 649-650.

Research output: Contribution to journalArticle

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T1 - Cobalt-Mediated Phosphorus-Aryl Bond Cleavage during Hydroformylatlon

AU - Dubois, Robert A.

AU - Garrou, Philip E.

AU - Lavln, Karen D.

AU - Allcock, Harry R.

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AB - Close examination of 1-hexene hydroformylation reactions catalyzed by cobalt carbonyl/triarylphosphine(PPh3 or P(p-MeC6H4)3, linked to PPh2-functionalized polystyrene or PPh2-functionalized (aryloxy) phosphazenes) has revealed a time-dependent decrease in catalytic activity due to a cobalt-mediated phosphorus-carbon bond cleavage. Benzene and benzyl alcohol were detected as the cleavage products. When olefin is omitted from the reaction, R2PH is formed. The detection of p-MeC6H4CH2OH indicates that oxidative addition of the P-aryl bond to Co is at least a partial contribution to the process. These results are relevant to transition-metal-triarylphosphine catalysis in general and put a new perspective on “immobilized” homogeneous catalysis.

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