Cobalt-Mediated Phosphorus-Aryl Bond Cleavage during Hydroformylatlon

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

doi:10.1021/om00082a032

Cobalt-Mediated Phosphorus-Aryl Bond Cleavage during Hydroformylatlon

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

Research output: Contribution to journal › Article › peer-review

49 Scopus citations

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 language	English (US)
Pages (from-to)	649-650
Number of pages	2
Journal	Organometallics
Volume	3
Issue number	4
DOIs	https://doi.org/10.1021/om00082a032
State	Published - Jan 1984

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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10.1021/om00082a032

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title = "Cobalt-Mediated Phosphorus-Aryl Bond Cleavage during Hydroformylatlon",

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.",

author = "Dubois, {Robert A.} and Garrou, {Philip E.} and Lavln, {Karen D.} and Allcock, {Harry R.}",

year = "1984",

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doi = "10.1021/om00082a032",

language = "English (US)",

volume = "3",

pages = "649--650",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "4",

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TY - JOUR

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.

PY - 1984/1

Y1 - 1984/1

N2 - 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.

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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JO - Organometallics

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Cobalt-Mediated Phosphorus-Aryl Bond Cleavage during Hydroformylatlon

Abstract

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