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Issue 27, 2015
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Bis(phenolate)amine-supported lanthanide borohydride complexes for styrene and trans-1,4-isoprene (co-)polymerisations

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Abstract

New bis(phenolate)amine-supported neodymium borohydride complexes and their previously reported samarium analogues were tested as catalysts for the polymerisation of styrene and isoprene. Reaction of Na2O2NL (L = py, OMe, NMe2) with Nd(BH4)3(THF)3 afforded the borohydride complexes Nd(O2NL)(BH4)(THF) (L = py (1-Nd), OMe (2-Nd), NMe2 (3-Nd)). Complex 1-Nd has shown a propensity to form phenolate-O-bridged dimer [Nd(μ-O2Npy)(BH4)]2 (1′-Nd) as previously observed with the samarium analogues Sm(O2NL)(BH4)(THF) (L = py or Pr). X-ray structures of 1′-Nd and 2-Nd were determined and are presented. The neodymium borohydride complexes 1-Nd to 3-Nd and their samarium analogues Sm(O2NL)(BH4)(THF)x (L = py (1-Sm), OMe (2-Sm), NMe2 (3-Sm), Pr (4-Sm)) were tested as catalysts for the polymerisation of isoprene and styrene in the presence of n-butylethylmagnesium (Mg(nBu)(Et)). All complexes were found to be active for the polymerisation of isoprene in these conditions, leading to polyisoprene up to 95.1% trans-1,4 stereoregular. They were also found to be active for the polymerisation of styrene leading to atactic polystyrene in all cases. Interestingly, samarium-based complexes were found to be more active than the neodymium ones toward this latter monomer, in sharp contrast to what is usually observed with rare earth borohydride complexes. The structure of both trans-polyisoprenes and polystyrenes obtained were studied in detail by MALDI-ToF analysis in order to better understand the polymerisation mechanisms. The coordinative chain transfer polymerisation (CCTP) of both monomers was further conducted using Mg(nBu)(Et) as transfer agent. Finally, the statistical copolymerisation of isoprene and styrene was examined using these catalytic systems, leading to the formation of poly[(trans-1,4-isoprene)-co-styrene] with up to 39% of styrene moieties inserted in a highly trans-1,4-stereoregular polyisoprene.

Graphical abstract: Bis(phenolate)amine-supported lanthanide borohydride complexes for styrene and trans-1,4-isoprene (co-)polymerisations

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Publication details

The article was received on 19 Jan 2015, accepted on 12 May 2015 and first published on 13 May 2015


Article type: Paper
DOI: 10.1039/C5DT00252D
Citation: Dalton Trans., 2015,44, 12312-12325
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    Bis(phenolate)amine-supported lanthanide borohydride complexes for styrene and trans-1,4-isoprene (co-)polymerisations

    F. Bonnet, H. E. Dyer, Y. El Kinani, C. Dietz, P. Roussel, M. Bria, M. Visseaux, P. Zinck and P. Mountford, Dalton Trans., 2015, 44, 12312
    DOI: 10.1039/C5DT00252D

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