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- W1992919196 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 and1H,13C1H,31P1H and17O1H NMR spectroscopic methods. Unlike their primary analogues, all the secondary complexes readily undergo a reversible carbonylation-decarbonylation reaction. The new alkyl complextrans-CH3O2CCH2Co(CO)3PPh3 (3) was characterized in solution, and exhibited remarkably different properties from the well-known homologuetrans-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 complextrans-CH3O2CCH2C(O)Co(CO)3PPh3 (4) was isolated as a stable solid, but smoothly decarbonylated in solution to3. Multinuclear NMR spectroscopic monitoring of this reaction suggested the intermediate formation ofcis-CH3O2CCH2Co(CO)3PPh3, providing the first direct evidence for alkyl migration in cobalt carbonyl complexes." @default.
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- W1992919196 title "Carbonylation-decarbonylation reactions of the carbomethoxymethylcobalt complexes CH3O2CCHRCo(CO)3L (R H, CH2CO2CH3; L CO, PPh3) and their acyl derivatives" @default.
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