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Issue 29, 2010
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Synthesis of samarium(II) borohydrides and their behaviour as initiators in styrene and ε-caprolactone polymerisation

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Abstract

The bisborohydrido samarium compound Sm(BH4)2(THF)2 (1) was prepared in high yield by comproportionation between Sm and 2 equivalents of Sm(BH4)3(THF)3. Reaction of 1 with KCp* (Cp* = C5Me5) afforded the half-sandwich Cp*Sm(BH4)(THF)2 (2). The 1H NMR borohydride resonances of both complexes, observed at very high field, are typical of divalent Sm compounds. X-Ray single crystal analysis revealed polymeric and dimeric molecular arrangements for 1 and 2, respectively. Complex 1 was found moderately active towards styrene polymerisation when activated with Al(iBu)3, or with a borate/Al combination, whereas 2 showed no activity. Ring-opening polymerisation of ε-caprolactone could be performed rapidly at room temperature with both initiators. Complex 2 leads to narrow polydispersities and higher activity. Two different mechanisms, by monoelectronic transfer or by insertion into the Sm–(BH4) bond can be proposed.

Graphical abstract: Synthesis of samarium(ii) borohydrides and their behaviour as initiators in styrene and ε-caprolactone polymerisation

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Publication details

The article was received on 26 Jan 2010, accepted on 31 Mar 2010 and first published on 06 May 2010


Article type: Paper
DOI: 10.1039/C001795G
Citation: Dalton Trans., 2010,39, 6761-6766
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    Synthesis of samarium(II) borohydrides and their behaviour as initiators in styrene and ε-caprolactone polymerisation

    F. Jaroschik, F. Bonnet, X. Le Goff, L. Ricard, F. Nief and M. Visseaux, Dalton Trans., 2010, 39, 6761
    DOI: 10.1039/C001795G

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