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Formation of anionic trifunctionalized metallalactones by nucleophilic addition at the β-carbonyl of a pyruvoyl ligand

Abstract : Anionic nucleophilic reagents Nu- = CH3O-, C2H5O-, t-BuO-, CH 3S-, and P(C6H5)2 - were found to react with (CO)4Fe(CO2CH 3)[C(O)C(O)CH3] to afford two isomers of anionic trifunctionalized metallalactones, (CO)3Fe[C(O)C(CH 3)(Nu)OC(O)](CO2CH3)-, whose formation resulted from an addition of the nucleophile to the β carbonyl of the pyruvoyl ligand. In this reaction, the metallacycle formation was found to occur by a further addition of the oxygen of the same β carbonyl on a terminal carbonyl. In acidic medium, these anionic complexes evolved into neutral metallalactones (CO)4Fe[C(O)C(CH3)(Nu)OC(O)] already obtained by performing the same reaction with pronucleophiles (Nu-H type reagents). Achievement of (CO)4Fe[C(O)C(=CH2)OC(O)] when the reaction was performed with t-BuO- could result from an intermediate formation of the enolate form of the pyruvoyl ligand [Fe]-C(O)-C(=CH2)-O- under basic conditions. © 2005 American Chemical Society.
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https://hal.univ-brest.fr/hal-01763749
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Submitted on : Wednesday, April 11, 2018 - 1:42:37 PM
Last modification on : Monday, August 31, 2020 - 3:20:12 PM

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Philippe Cabon, R. Rumin, J.Y. Salaün, Smail Triki, H. Des Abbayes. Formation of anionic trifunctionalized metallalactones by nucleophilic addition at the β-carbonyl of a pyruvoyl ligand. Organometallics, American Chemical Society, 2005, 24 (7), pp.1709-1717. ⟨10.1021/om049030r⟩. ⟨hal-01763749⟩

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