Carbonylation-decarbonylation reactions of the carbomethoxymethylcobalt complexes CH3O2CCHRCO(CO)3l (R = H, CH2CO2CH3; L = CO, PPh3) and their acyl derivatives

István Kovács, Gábor Szalontai, F. Ungváry

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Abstract

The primary and secondary alkyl- and acylcobalt carbonyl complexes CH3O2CCHRCo(CO)3L and CH3O2CCHRC(O)Co(CO)3L (R = H or CH2CO2CH3; L = CO, PPh3) (1-8) have been prepared and studied by a variety of IR and 1H, 13C{1H}, 31P{1H} and 17O{1H} NMR spectroscopic methods. Unlike their primary analogues, all the secondary complexes readily undergo a reversible carbonylation-decarbonylation reaction. The new alkyl complex trans-CH3O2CCH2Co(CO)3PPh3 (3) was characterized in solution, and exhibited remarkably different properties from the well-known homologue trans-CH3CH2O2CCH2Co(CO)3PPh3, i.e. it readily decomposes to [Co(CO)3PPh3]2, suggesting homolytic dissociation of the carbon-cobalt bond, and its IR spectrum exhibits an organic ν(CO) absorbance at an unusually low frequency, pointing to an oxygen-cobalt interaction. The corresponding acyl complex trans-CH3O2CCH2C(O)Co(CO)3PPh3 (4) was isolated as a stable solid, but smoothly decarbonylated in solution to 3. Multinuclear NMR spectroscopic monitoring of this reaction suggested the intermediate formation of cis-CH3O2CCH2Co(CO)3PPh3, providing the first direct evidence for alkyl migration in cobalt carbonyl complexes.

Original languageEnglish
Pages (from-to)115-123
Number of pages9
JournalJournal of Organometallic Chemistry
Volume524
Issue number1-2
Publication statusPublished - Nov 1 1996

Fingerprint

Carbonylation
Cobalt
cobalt
Derivatives
Nuclear magnetic resonance
Biomolecular Nuclear Magnetic Resonance
nuclear magnetic resonance
Carbon
dissociation
analogs
Oxygen
low frequencies
Monitoring
carbon
oxygen
interactions

Keywords

  • Acyl
  • Alkyl
  • Carbonyl
  • Carbonylation
  • Cobalt
  • Decarbonylation

ASJC Scopus subject areas

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

Cite this

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title = "Carbonylation-decarbonylation reactions of the carbomethoxymethylcobalt complexes CH3O2CCHRCO(CO)3l (R = H, CH2CO2CH3; L = CO, PPh3) and their acyl derivatives",
abstract = "The primary and secondary alkyl- and acylcobalt carbonyl complexes CH3O2CCHRCo(CO)3L and CH3O2CCHRC(O)Co(CO)3L (R = H or CH2CO2CH3; L = CO, PPh3) (1-8) have been prepared and studied by a variety of IR and 1H, 13C{1H}, 31P{1H} and 17O{1H} NMR spectroscopic methods. Unlike their primary analogues, all the secondary complexes readily undergo a reversible carbonylation-decarbonylation reaction. The new alkyl complex trans-CH3O2CCH2Co(CO)3PPh3 (3) was characterized in solution, and exhibited remarkably different properties from the well-known homologue trans-CH3CH2O2CCH2Co(CO)3PPh3, i.e. it readily decomposes to [Co(CO)3PPh3]2, suggesting homolytic dissociation of the carbon-cobalt bond, and its IR spectrum exhibits an organic ν(CO) absorbance at an unusually low frequency, pointing to an oxygen-cobalt interaction. The corresponding acyl complex trans-CH3O2CCH2C(O)Co(CO)3PPh3 (4) was isolated as a stable solid, but smoothly decarbonylated in solution to 3. Multinuclear NMR spectroscopic monitoring of this reaction suggested the intermediate formation of cis-CH3O2CCH2Co(CO)3PPh3, providing the first direct evidence for alkyl migration in cobalt carbonyl complexes.",
keywords = "Acyl, Alkyl, Carbonyl, Carbonylation, Cobalt, Decarbonylation",
author = "Istv{\'a}n Kov{\'a}cs and G{\'a}bor Szalontai and F. Ungv{\'a}ry",
year = "1996",
month = "11",
day = "1",
language = "English",
volume = "524",
pages = "115--123",
journal = "Journal of Organometallic Chemistry",
issn = "0022-328X",
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TY - JOUR

T1 - Carbonylation-decarbonylation reactions of the carbomethoxymethylcobalt complexes CH3O2CCHRCO(CO)3l (R = H, CH2CO2CH3; L = CO, PPh3) and their acyl derivatives

AU - Kovács, István

AU - Szalontai, Gábor

AU - Ungváry, F.

PY - 1996/11/1

Y1 - 1996/11/1

N2 - The primary and secondary alkyl- and acylcobalt carbonyl complexes CH3O2CCHRCo(CO)3L and CH3O2CCHRC(O)Co(CO)3L (R = H or CH2CO2CH3; L = CO, PPh3) (1-8) have been prepared and studied by a variety of IR and 1H, 13C{1H}, 31P{1H} and 17O{1H} NMR spectroscopic methods. Unlike their primary analogues, all the secondary complexes readily undergo a reversible carbonylation-decarbonylation reaction. The new alkyl complex trans-CH3O2CCH2Co(CO)3PPh3 (3) was characterized in solution, and exhibited remarkably different properties from the well-known homologue trans-CH3CH2O2CCH2Co(CO)3PPh3, i.e. it readily decomposes to [Co(CO)3PPh3]2, suggesting homolytic dissociation of the carbon-cobalt bond, and its IR spectrum exhibits an organic ν(CO) absorbance at an unusually low frequency, pointing to an oxygen-cobalt interaction. The corresponding acyl complex trans-CH3O2CCH2C(O)Co(CO)3PPh3 (4) was isolated as a stable solid, but smoothly decarbonylated in solution to 3. Multinuclear NMR spectroscopic monitoring of this reaction suggested the intermediate formation of cis-CH3O2CCH2Co(CO)3PPh3, providing the first direct evidence for alkyl migration in cobalt carbonyl complexes.

AB - The primary and secondary alkyl- and acylcobalt carbonyl complexes CH3O2CCHRCo(CO)3L and CH3O2CCHRC(O)Co(CO)3L (R = H or CH2CO2CH3; L = CO, PPh3) (1-8) have been prepared and studied by a variety of IR and 1H, 13C{1H}, 31P{1H} and 17O{1H} NMR spectroscopic methods. Unlike their primary analogues, all the secondary complexes readily undergo a reversible carbonylation-decarbonylation reaction. The new alkyl complex trans-CH3O2CCH2Co(CO)3PPh3 (3) was characterized in solution, and exhibited remarkably different properties from the well-known homologue trans-CH3CH2O2CCH2Co(CO)3PPh3, i.e. it readily decomposes to [Co(CO)3PPh3]2, suggesting homolytic dissociation of the carbon-cobalt bond, and its IR spectrum exhibits an organic ν(CO) absorbance at an unusually low frequency, pointing to an oxygen-cobalt interaction. The corresponding acyl complex trans-CH3O2CCH2C(O)Co(CO)3PPh3 (4) was isolated as a stable solid, but smoothly decarbonylated in solution to 3. Multinuclear NMR spectroscopic monitoring of this reaction suggested the intermediate formation of cis-CH3O2CCH2Co(CO)3PPh3, providing the first direct evidence for alkyl migration in cobalt carbonyl complexes.

KW - Acyl

KW - Alkyl

KW - Carbonyl

KW - Carbonylation

KW - Cobalt

KW - Decarbonylation

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M3 - Article

AN - SCOPUS:0030295583

VL - 524

SP - 115

EP - 123

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

SN - 0022-328X

IS - 1-2

ER -