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Issue 10, 2010
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Neutral ansa-bis(fluorenyl)silane neodymium borohydrides: synthesis, structural study and behaviour as catalysts in butadiene–ethylenecopolymerisation

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Abstract

The reaction of silylene-bridged bis(fluorenyl)dipotassium salts with neodymium tris(borohydride) afforded new neutral ansa-bis(fluorenyl)silane neodymium borohydrides: (Flu2SiR2)Nd(BH4)(THF) [R2 = Me2, Et2, (CH2)3, Me(Ph), Flu = C13H8] that were better characterised and more soluble than the previously described anionic [(Flu2SiMe2)Nd(BH4)2]. The X-ray structures of three of these complexes were determined, and their solid-state geometrical parameters are very similar, despite the ring strain introduced by the silacyclobutane bridge in [Flu2Si(CH2)3]Nd(BH4)(THF). The main geometrical features were satisfactorily reproduced by DFT calculations. The catalytic activity of the title complexes in ethylenebutadiene copolymerisation reactions was assessed and compared to that of the reported activity of [(Flu2SiMe2)Nd(BH4)2] under similar conditions. From these results it can be concluded that the cyclo-copolymerisation of ethylene with butadiene is characteristic of a catalyst featuring silylene-bridged bis(fluorenyl) ligands around neodymium, and appears to be independent of the substituents at the silicon atom.

Graphical abstract: Neutral ansa-bis(fluorenyl)silane neodymium borohydrides: synthesis, structural study and behaviour as catalysts in butadiene–ethylene copolymerisation

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Publication details

The article was received on 14 Apr 2010, accepted on 26 May 2010 and first published on 29 Jun 2010


Article type: Paper
DOI: 10.1039/C0NJ00274G
New J. Chem., 2010,34, 2290-2297

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    Neutral ansa-bis(fluorenyl)silane neodymium borohydrides: synthesis, structural study and behaviour as catalysts in butadieneethylene copolymerisation

    G. Cortial, X. Le Goff, M. Bousquié, C. Boisson, P. Le Floch, F. Nief and J. Thuilliez, New J. Chem., 2010, 34, 2290
    DOI: 10.1039/C0NJ00274G

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