Dialkenylmagnesium Compounds in Coordinative Chain Transfer Polymerization of Ethylene. Reversible Chain Transfer Agents and Tools To Probe Catalyst Selectivities toward Ring Formation - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Organometallics Année : 2018

Dialkenylmagnesium Compounds in Coordinative Chain Transfer Polymerization of Ethylene. Reversible Chain Transfer Agents and Tools To Probe Catalyst Selectivities toward Ring Formation

Résumé

A range of dialkenylmagnesium compounds ([CH2═CH(CH2)n]2Mg; n = 1–6) were synthesized and used as chain transfer agents (CTA) with either (C5Me5)2NdCl2Li(OEt2)2 (1) or [Me2Si(C13H8)2Nd(BH4)2Li(thf)]2 (2) neodymium precursors for the polymerization of ethylene. In all cases, the systems followed a controlled coordinative chain transfer polymerization mechanism. The intramolecular insertion of the vinyl group on the CTA in growing chains is possible and led to the formation of cyclopentyl, cyclohexyl, and possibly cycloheptyl chain ends. While the production of cyclopentyl- or cyclohexyl-capped polyethylene chains can be quantitative (n = 2–5), the integrity of this double bond can also be kept if n is higher than 6. In comparison to 1/CTA catalytic systems, 2/CTA catalytic systems showed a higher propensity to produce cycloalkyl chain ends. This was ascribed to the lower steric demand around the active site, as shown by DFT calculations. In addition, the formation of bis(cyclopentylmethyl)magnesium from dipentenylmagnesium using a catalytic amount of 2 was shown.

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Chimie
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Dates et versions

hal-01874330 , version 1 (14-09-2018)

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Citer

Islem Belaid, Marie-Noëlle Poradowski, Samira Bouaouli, Julien Thuilliez, Lionel Perrin, et al.. Dialkenylmagnesium Compounds in Coordinative Chain Transfer Polymerization of Ethylene. Reversible Chain Transfer Agents and Tools To Probe Catalyst Selectivities toward Ring Formation. Organometallics, 2018, 37 (10), pp.1546 - 1554. ⟨10.1021/acs.organomet.8b00127⟩. ⟨hal-01874330⟩
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