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Issue 42, 2007
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Mono-phosphacyclopentadienyl bis(tetramethylaluminate) lanthanide complexes

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Homoleptic complexes Ln(AlMe4)3 (Ln = La, Nd) can be straightforwardly utilized in salt metathetic exchange reactions with potassium 2,3,4,5-tetramethylphospholide (KTmp) or 3,4-dimethyl-2,5-bis(trimethylsilyl)phospholide (KDsp) affording monophosphacyclopentadienyl hydrocarbyl complexes (η5-PC4Me4)Ln(AlMe4)2 and [η5-PC4Me2(SiMe3)2]Ln(AlMe4)2 (Ln = La, Nd). The solid-state structures reveal distinct metal size effects as evidenced by X-ray diffraction analyses of monomeric neodymium Tmp and Dsp derivatives as well as the dimeric lanthanum Tmp complex. Dimerization is accomplished by intermolecular P → La donor contacts. Upon activation with [PhMe2NH][B(C6F5)4] the monophosphacyclopentadienyl complexes initiate the polymerization of isoprene producing 1,4-trans-polyisoprene (tPIP > 87%) with moderate activity (≈30 kgPIP molLn−1 h−1).

Graphical abstract: Mono-phosphacyclopentadienyl bis(tetramethylaluminate) lanthanide complexes

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The article was received on 25 Jun 2007, accepted on 09 Aug 2007 and first published on 29 Aug 2007

Article type: Paper
DOI: 10.1039/B709633J
Citation: Dalton Trans., 2007,0, 4866-4870
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    Mono-phosphacyclopentadienyl bis(tetramethylaluminate) lanthanide complexes

    E. Le Roux, F. Nief, F. Jaroschik, K. W. Törnroos and R. Anwander, Dalton Trans., 2007, 0, 4866
    DOI: 10.1039/B709633J

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