Triphenylphosphane-modified cobalt catalysts for the selective carbonylation of ethyl diazoacetate

Neszta Ungvári, Eszter Fördos, János Balogh, Tamás Kégl, László Párkányi, Ferenc Ungváry

Research output: Contribution to journalArticle

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Abstract

The triphenylphosphane-substituted carbonyl cobalt complexes Co 2(CO)7(PPh3), Co2(CO) 6(CHCO2Et)(PPh3), and [Co(CO) 3(PPh3)2][Co(CO)4] were found to be more effective precatalysts in the carbonylation of ethyl diazoacetate under atmospheric pressure of carbon monoxide at 10 °C in dichloromethane solution than the parent Co2(CO)8 and Co2(CO) 7(CHCO2Et) complexes. The highly reactive (ethoxycarbonyl)ketene is the primary product of the catalytic carbonylation, which dimerizes in the absence of a proper scavenger. In the presence of ethanol as the trapping reagent diethyl malonate is the final product of the carbonylation reaction. The formation of (ethoxycarbonyl)ketene using the catalyst precursor Co2(CO)7(PPh3) occurs in a catalytic cycle, where Co2(CO)6(PPh3) and Co2(CO)6(CHCO2Et)(PPh3) are the repeating species. The 16e species Co2(CO)6(PPh 3) is involved in the deazotization of ethyl diazoacetate, and Co2(CO)6(CHCO2Et)(PPh3) leads to the (ethoxycarbonyl)ketene formation. In the absence of carbon monoxide or at low CO concentration the reaction of Co2(CO)6(CHCO 2Et)(PPh3) with ethyl diazoacetate is the source of Co2(CO)5(CHCO2Et)2(PPh3), which is not an active catalyst for the carbonylation of ethyl diazoacetate. Using [Co(CO)3(PPh3)2][Co(CO)4] as the catalyst precursor, the intermediary formation of [Co(CO) 3(PPh3)2][Co(CO)3(O=C=CHCO 2Et)] through radical pairs is assumed. Substituting PPh3 in Co2(CO)7(PPh3), Co2(CO) 6(CHCO2Et)(PPh3), and [Co(CO) 3(PPh3)2][Co(CO)4] by polymer-bound PPh3 results in active and reusable catalysts for the selective carbonylation of ethyl diazoacetate in dichloromethane solution at 40 °C and 11 bar of pressure with up to 5.1 mol of product/((mol of catalyst) h) turnover frequency.

Original languageEnglish
Pages (from-to)3837-3851
Number of pages15
JournalOrganometallics
Volume29
Issue number17
DOIs
Publication statusPublished - 13 Sep 2010
Externally publishedYes

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Carbonylation
Cobalt
cobalt
catalysts
Catalysts
Methylene Chloride
Carbon Monoxide
carbon monoxide
products
Atmospheric pressure
reagents
low concentrations
atmospheric pressure
Polymers
ethyl alcohol
Ethanol
trapping
diazoacetic ester
cycles
polymers

ASJC Scopus subject areas

  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Triphenylphosphane-modified cobalt catalysts for the selective carbonylation of ethyl diazoacetate. / Ungvári, Neszta; Fördos, Eszter; Balogh, János; Kégl, Tamás; Párkányi, László; Ungváry, Ferenc.

In: Organometallics, Vol. 29, No. 17, 13.09.2010, p. 3837-3851.

Research output: Contribution to journalArticle

Ungvári, N, Fördos, E, Balogh, J, Kégl, T, Párkányi, L & Ungváry, F 2010, 'Triphenylphosphane-modified cobalt catalysts for the selective carbonylation of ethyl diazoacetate', Organometallics, vol. 29, no. 17, pp. 3837-3851. https://doi.org/10.1021/om100480v
Ungvári, Neszta ; Fördos, Eszter ; Balogh, János ; Kégl, Tamás ; Párkányi, László ; Ungváry, Ferenc. / Triphenylphosphane-modified cobalt catalysts for the selective carbonylation of ethyl diazoacetate. In: Organometallics. 2010 ; Vol. 29, No. 17. pp. 3837-3851.
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abstract = "The triphenylphosphane-substituted carbonyl cobalt complexes Co 2(CO)7(PPh3), Co2(CO) 6(CHCO2Et)(PPh3), and [Co(CO) 3(PPh3)2][Co(CO)4] were found to be more effective precatalysts in the carbonylation of ethyl diazoacetate under atmospheric pressure of carbon monoxide at 10 °C in dichloromethane solution than the parent Co2(CO)8 and Co2(CO) 7(CHCO2Et) complexes. The highly reactive (ethoxycarbonyl)ketene is the primary product of the catalytic carbonylation, which dimerizes in the absence of a proper scavenger. In the presence of ethanol as the trapping reagent diethyl malonate is the final product of the carbonylation reaction. The formation of (ethoxycarbonyl)ketene using the catalyst precursor Co2(CO)7(PPh3) occurs in a catalytic cycle, where Co2(CO)6(PPh3) and Co2(CO)6(CHCO2Et)(PPh3) are the repeating species. The 16e species Co2(CO)6(PPh 3) is involved in the deazotization of ethyl diazoacetate, and Co2(CO)6(CHCO2Et)(PPh3) leads to the (ethoxycarbonyl)ketene formation. In the absence of carbon monoxide or at low CO concentration the reaction of Co2(CO)6(CHCO 2Et)(PPh3) with ethyl diazoacetate is the source of Co2(CO)5(CHCO2Et)2(PPh3), which is not an active catalyst for the carbonylation of ethyl diazoacetate. Using [Co(CO)3(PPh3)2][Co(CO)4] as the catalyst precursor, the intermediary formation of [Co(CO) 3(PPh3)2][Co(CO)3(O=C=CHCO 2Et)] through radical pairs is assumed. Substituting PPh3 in Co2(CO)7(PPh3), Co2(CO) 6(CHCO2Et)(PPh3), and [Co(CO) 3(PPh3)2][Co(CO)4] by polymer-bound PPh3 results in active and reusable catalysts for the selective carbonylation of ethyl diazoacetate in dichloromethane solution at 40 °C and 11 bar of pressure with up to 5.1 mol of product/((mol of catalyst) h) turnover frequency.",
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AU - Ungvári, Neszta

AU - Fördos, Eszter

AU - Balogh, János

AU - Kégl, Tamás

AU - Párkányi, László

AU - Ungváry, Ferenc

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N2 - The triphenylphosphane-substituted carbonyl cobalt complexes Co 2(CO)7(PPh3), Co2(CO) 6(CHCO2Et)(PPh3), and [Co(CO) 3(PPh3)2][Co(CO)4] were found to be more effective precatalysts in the carbonylation of ethyl diazoacetate under atmospheric pressure of carbon monoxide at 10 °C in dichloromethane solution than the parent Co2(CO)8 and Co2(CO) 7(CHCO2Et) complexes. The highly reactive (ethoxycarbonyl)ketene is the primary product of the catalytic carbonylation, which dimerizes in the absence of a proper scavenger. In the presence of ethanol as the trapping reagent diethyl malonate is the final product of the carbonylation reaction. The formation of (ethoxycarbonyl)ketene using the catalyst precursor Co2(CO)7(PPh3) occurs in a catalytic cycle, where Co2(CO)6(PPh3) and Co2(CO)6(CHCO2Et)(PPh3) are the repeating species. The 16e species Co2(CO)6(PPh 3) is involved in the deazotization of ethyl diazoacetate, and Co2(CO)6(CHCO2Et)(PPh3) leads to the (ethoxycarbonyl)ketene formation. In the absence of carbon monoxide or at low CO concentration the reaction of Co2(CO)6(CHCO 2Et)(PPh3) with ethyl diazoacetate is the source of Co2(CO)5(CHCO2Et)2(PPh3), which is not an active catalyst for the carbonylation of ethyl diazoacetate. Using [Co(CO)3(PPh3)2][Co(CO)4] as the catalyst precursor, the intermediary formation of [Co(CO) 3(PPh3)2][Co(CO)3(O=C=CHCO 2Et)] through radical pairs is assumed. Substituting PPh3 in Co2(CO)7(PPh3), Co2(CO) 6(CHCO2Et)(PPh3), and [Co(CO) 3(PPh3)2][Co(CO)4] by polymer-bound PPh3 results in active and reusable catalysts for the selective carbonylation of ethyl diazoacetate in dichloromethane solution at 40 °C and 11 bar of pressure with up to 5.1 mol of product/((mol of catalyst) h) turnover frequency.

AB - The triphenylphosphane-substituted carbonyl cobalt complexes Co 2(CO)7(PPh3), Co2(CO) 6(CHCO2Et)(PPh3), and [Co(CO) 3(PPh3)2][Co(CO)4] were found to be more effective precatalysts in the carbonylation of ethyl diazoacetate under atmospheric pressure of carbon monoxide at 10 °C in dichloromethane solution than the parent Co2(CO)8 and Co2(CO) 7(CHCO2Et) complexes. The highly reactive (ethoxycarbonyl)ketene is the primary product of the catalytic carbonylation, which dimerizes in the absence of a proper scavenger. In the presence of ethanol as the trapping reagent diethyl malonate is the final product of the carbonylation reaction. The formation of (ethoxycarbonyl)ketene using the catalyst precursor Co2(CO)7(PPh3) occurs in a catalytic cycle, where Co2(CO)6(PPh3) and Co2(CO)6(CHCO2Et)(PPh3) are the repeating species. The 16e species Co2(CO)6(PPh 3) is involved in the deazotization of ethyl diazoacetate, and Co2(CO)6(CHCO2Et)(PPh3) leads to the (ethoxycarbonyl)ketene formation. In the absence of carbon monoxide or at low CO concentration the reaction of Co2(CO)6(CHCO 2Et)(PPh3) with ethyl diazoacetate is the source of Co2(CO)5(CHCO2Et)2(PPh3), which is not an active catalyst for the carbonylation of ethyl diazoacetate. Using [Co(CO)3(PPh3)2][Co(CO)4] as the catalyst precursor, the intermediary formation of [Co(CO) 3(PPh3)2][Co(CO)3(O=C=CHCO 2Et)] through radical pairs is assumed. Substituting PPh3 in Co2(CO)7(PPh3), Co2(CO) 6(CHCO2Et)(PPh3), and [Co(CO) 3(PPh3)2][Co(CO)4] by polymer-bound PPh3 results in active and reusable catalysts for the selective carbonylation of ethyl diazoacetate in dichloromethane solution at 40 °C and 11 bar of pressure with up to 5.1 mol of product/((mol of catalyst) h) turnover frequency.

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