Phosphine Addition to Pyruvoyl Ligands of Iron Complexes: Formation of Zwitterionic Metallalactones

Abstract : Tertiary phosphines react, at −80 °C, with the pyruvoyl-substituted iron complex (CO)4Fe[C(O)C(O)CH3](CO2CH3) (1) to give rise to phosphonium-substituted metallalactones fac-(CO)3tiebar above startFe[C(O)C(CH3)(PR3)Otiebar above endC(O)](CO2CH3) (2). These zwitterionic compounds are formed by an initial addition of the phosphine to the noncoordinated carbonyl of the pyruvoyl unit followed by the addition of the oxygen of this C═O on a terminal carbonyl. They display an anionic metal center substituted by three organic ligands and a positive charge located on a phosphonium group. Attempts to extend the reaction to the related cationic pentacarbonyl pyruvoyl-substituted iron complex failed, as no reaction was observed with the same reagents. However, the expected products of these reactions, cationic phosphonium metallalactones {(CO)4tiebar above startFe[C(O)C(CH3)(PR3)Otiebar above endC(O)]}+, were obtained by acidic dissociation of the alkoxycarbonyl ligand of the relevant zwitterionic metallalactones.
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Article dans une revue
Organometallics, American Chemical Society, 2009, 28 (1), pp.216 - 224. 〈10.1021/om800804b〉
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http://hal.univ-brest.fr/hal-01578077
Contributeur : Nicolas Renard <>
Soumis le : lundi 28 août 2017 - 16:15:48
Dernière modification le : jeudi 11 janvier 2018 - 06:17:06

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J. Y. Salaün, R. Rumin, F. Setifi, Smail Triki, Paul-Alain Jaffres. Phosphine Addition to Pyruvoyl Ligands of Iron Complexes: Formation of Zwitterionic Metallalactones. Organometallics, American Chemical Society, 2009, 28 (1), pp.216 - 224. 〈10.1021/om800804b〉. 〈hal-01578077〉

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