Cyclization of the pyruvyl(methoxycarbonyl)tetracarbonyliron complex cis-(CO)4Fe[C(O)C(O)CH3](CO2CH3) induced by pronucleophile reagents - Université de Bretagne Occidentale Access content directly
Journal Articles Organometallics Year : 2002

Cyclization of the pyruvyl(methoxycarbonyl)tetracarbonyliron complex cis-(CO)4Fe[C(O)C(O)CH3](CO2CH3) induced by pronucleophile reagents

P. Gabon
  • Function : Author
M. Sellin
  • Function : Author
J.-Y. Salaün
  • Function : Author
M.M. Kubicki
  • Function : Author

Abstract

Two iron complexes, cis-(CO)4Fe[C(O)C(O)CH3](CO2CH3) (1a) and cis-(CO)4Fe[C(O)CO2-CH2] [C(O)CH2] (3), are reported. Each complex can be considered as a λ-keto ester with a metal atom inserted into the chain linking its two organic groups. 1a is the only one found to evolve thermally, similarly to organic λ-keto esters, into the methoxy metallalactone (CO)4FeC(O)C(CH3)(OCH3)OC(O) (2a). This reaction is not reversible and does not require any acid or alkaline catalysis. The process does not result from a spontaneous dissociation of the methoxycarbonyl ligand of la but from an associative intra or intermolecular mechanism. A similar process can also be induced by pronucleophile reagents, and it affords a series of substituted metallalactones: (CO)4FeC(O)C(CH3)(Nu)OC(O) (Nu = OCH3 (2a), OC2H5 (2b), SC2H5 (2c), P(C6H5)2 (2d), P(C6H11)2 (2e)). Complex 2e has been characterized structurally. These substituted lactones are formed by nucleophilic attack of the reagent at the pyruvyl β-carbonyl followed by carbonylate attack on the alkoxycarbonyl ligand.

Dates and versions

hal-01771340 , version 1 (19-04-2018)

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P. Gabon, M. Sellin, J.-Y. Salaün, Véronique Patinec, H. Des Abbayes, et al.. Cyclization of the pyruvyl(methoxycarbonyl)tetracarbonyliron complex cis-(CO)4Fe[C(O)C(O)CH3](CO2CH3) induced by pronucleophile reagents. Organometallics, 2002, 21, pp.2196--2202. ⟨10.1021/om010989d⟩. ⟨hal-01771340⟩
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