Cobalt Hydroformylation Catalyst Supported on a Phosphinated Polyphosphazene. Identification of Phosphorus-Carbon Bond Cleavage as Mode of Catalyst Deactivation

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

Research output: Contribution to journalArticle

54 Citations (Scopus)

Abstract

The interaction of Co2(CO)8 with [NP(OPh)L7(OC6H4PPh2)03]n(1), N3P3(OPh)5(OC6H4PPh2) (2), PPh2-linked polystyrene (3), or triarylphosphine [PPh3, P(p-CH3C6H4)3] yielded species of the type Co2(CO)7PR3, [CO(CO) 3PR3]2, and [Co(CO)3(PR3)2]+Co(CO)4~ as identified by infrared spectroscopy and 31P NMR. Catalysts derived from 1 were expected to have higher thermal stability based on the inherent thermal stability of 1 vs. 3. A study of the catalyst system 1 /Co2(CO)8 for 1-hexene hydroformylation revealed an initial activity equal to its homogeneous analogue. This has been rationalized as due to cleavage of cross-linking P-Co-P sites during reaction with CO/H2 to give soluble hydride HCo(CO)3PR3 type species. All of the catalysts also revealed a time-dependent decrease in catalytic activity, due to a cobalt-mediated phosphorus-carbon bond cleavage. Benzene, toluene, benzyl alcohol, and p-MeC6H4CH2OH were detected as primary cleavage products. When olefin was omitted from these reactions, R2PH was observed.

Original languageEnglish (US)
Pages (from-to)460-466
Number of pages7
JournalOrganometallics
Volume5
Issue number3
DOIs
StatePublished - Jan 1 1986

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Hydroformylation
Catalyst deactivation
Cobalt
Catalyst supports
deactivation
Phosphorus
phosphorus
cleavage
cobalt
Carbon
catalysts
Catalysts
carbon
Thermodynamic stability
thermal stability
Benzyl Alcohol
hexenes
Polystyrenes
Toluene
Alkenes

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

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title = "Cobalt Hydroformylation Catalyst Supported on a Phosphinated Polyphosphazene. Identification of Phosphorus-Carbon Bond Cleavage as Mode of Catalyst Deactivation",
abstract = "The interaction of Co2(CO)8 with [NP(OPh)L7(OC6H4PPh2)03]n(1), N3P3(OPh)5(OC6H4PPh2) (2), PPh2-linked polystyrene (3), or triarylphosphine [PPh3, P(p-CH3C6H4)3] yielded species of the type Co2(CO)7PR3, [CO(CO) 3PR3]2, and [Co(CO)3(PR3)2]+Co(CO)4~ as identified by infrared spectroscopy and 31P NMR. Catalysts derived from 1 were expected to have higher thermal stability based on the inherent thermal stability of 1 vs. 3. A study of the catalyst system 1 /Co2(CO)8 for 1-hexene hydroformylation revealed an initial activity equal to its homogeneous analogue. This has been rationalized as due to cleavage of cross-linking P-Co-P sites during reaction with CO/H2 to give soluble hydride HCo(CO)3PR3 type species. All of the catalysts also revealed a time-dependent decrease in catalytic activity, due to a cobalt-mediated phosphorus-carbon bond cleavage. Benzene, toluene, benzyl alcohol, and p-MeC6H4CH2OH were detected as primary cleavage products. When olefin was omitted from these reactions, R2PH was observed.",
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Cobalt Hydroformylation Catalyst Supported on a Phosphinated Polyphosphazene. Identification of Phosphorus-Carbon Bond Cleavage as Mode of Catalyst Deactivation. / Dubois, Robert A.; Garrou, Philip E.; Lavin, Karen D.; Allcock, Harry R.

In: Organometallics, Vol. 5, No. 3, 01.01.1986, p. 460-466.

Research output: Contribution to journalArticle

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T1 - Cobalt Hydroformylation Catalyst Supported on a Phosphinated Polyphosphazene. Identification of Phosphorus-Carbon Bond Cleavage as Mode of Catalyst Deactivation

AU - Dubois, Robert A.

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AU - Allcock, Harry R.

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AB - The interaction of Co2(CO)8 with [NP(OPh)L7(OC6H4PPh2)03]n(1), N3P3(OPh)5(OC6H4PPh2) (2), PPh2-linked polystyrene (3), or triarylphosphine [PPh3, P(p-CH3C6H4)3] yielded species of the type Co2(CO)7PR3, [CO(CO) 3PR3]2, and [Co(CO)3(PR3)2]+Co(CO)4~ as identified by infrared spectroscopy and 31P NMR. Catalysts derived from 1 were expected to have higher thermal stability based on the inherent thermal stability of 1 vs. 3. A study of the catalyst system 1 /Co2(CO)8 for 1-hexene hydroformylation revealed an initial activity equal to its homogeneous analogue. This has been rationalized as due to cleavage of cross-linking P-Co-P sites during reaction with CO/H2 to give soluble hydride HCo(CO)3PR3 type species. All of the catalysts also revealed a time-dependent decrease in catalytic activity, due to a cobalt-mediated phosphorus-carbon bond cleavage. Benzene, toluene, benzyl alcohol, and p-MeC6H4CH2OH were detected as primary cleavage products. When olefin was omitted from these reactions, R2PH was observed.

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