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Issue 32, 2010
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Coordination chemistry with phosphine and phosphine oxide-substituted hydroxyferrocenes

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Abstract

New unsymmetrical hydroxyferrocenes were synthesised from dibromoferrocene. The oxygen heteroatom was introduced via lithiation and quenching with bis-trimethylsilylperoxide followed by hydrolysis to unmask the hydroxyl functionality. The coordination chemistry of 1′-(diphenylphosphino)-1-hydroxyferrocene 2 was explored with palladium and rhodium precursors. A dinuclear palladium methyl complex with bridging ferrocenyloxo groups was obtained from the reaction between 2 and (cyclooctadiene)methylchloropalladium(II). With tetracarbonyldichlorodirhodium(I), two complexes were isolated. The major product was a bis ligand cis phosphine ligated complex with one ligand bound in a chelating mode and one with a pendant hydroxyl group. A minor product was crystallographically characterised as a dinuclear ferrocenyloxo-bridged rhodium carbonyl complex. The coordination chemistry of 2 and the corresponding phosphine oxide 3 was examined with group 4 metals and the resulting complexes examined as ethylene polymerisation catalysts. The ligands were found to bind in either a chelating fashion or with pendant phosphine donors. In all cases, low to moderately active ethylene polymerisation catalysts were found. The catalysts were very unstable and catalyst residues were observed in the isolated polymer indicating a short catalyst lifetime.

Graphical abstract: Coordination chemistry with phosphine and phosphine oxide-substituted hydroxyferrocenes

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Publication details

The article was received on 03 Mar 2010, accepted on 01 Jun 2010 and first published on 07 Jul 2010


Article type: Paper
DOI: 10.1039/C0DT00061B
Citation: Dalton Trans., 2010,39, 7540-7546
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    Coordination chemistry with phosphine and phosphine oxide-substituted hydroxyferrocenes

    R. C. J. Atkinson, V. C. Gibson, N. J. Long and A. J. P. White, Dalton Trans., 2010, 39, 7540
    DOI: 10.1039/C0DT00061B

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