Mechanistic Insights of the Initiation Process of the Ring-Opening Polymerization of epsilon-Caprolactone by Divalent Sm(BH4)2THF2 with DFT: Concerted or Oxidative Reaction? - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Organometallics Année : 2011

Mechanistic Insights of the Initiation Process of the Ring-Opening Polymerization of epsilon-Caprolactone by Divalent Sm(BH4)2THF2 with DFT: Concerted or Oxidative Reaction?

Résumé

Concerted and oxidative mechanisms for the initiation of the ROP of ε-caprolactone by divalent Sm(BH4)2(THF)2 have been computed at the DFT level and compared with experimental data. The concerted polymerization pathway is proposed to occur via divalent [Sm]-(BH4) active species through classical O-acyl cleavage, leading to α,ω-dihydroxy telechelic polycaprolactone, which is fully compatible with chain end groups observed for low-Mn samples prepared with Sm(BH4)2(THF)2. Although it is calculated to be favorable, the oxidative route affording radical species is not in accordance with these experimental results, unless one considers transfer reactions with the solvent.
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hal-00694171 , version 1 (03-05-2012)

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Christophe Iftner, Fanny Bonnet, François Nief, Marc Visseaux, Laurent Maron. Mechanistic Insights of the Initiation Process of the Ring-Opening Polymerization of epsilon-Caprolactone by Divalent Sm(BH4)2THF2 with DFT: Concerted or Oxidative Reaction?. Organometallics, 2011, 30 (17), pp.4482-4485. ⟨10.1021/om200512g⟩. ⟨hal-00694171⟩
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