Zirconium hydrocarbyl chemisorption on sulfated metal oxides: New supports, chemisorption pathways, and implications for catalysis

Christopher P. Nicholas, Tobin J. Marks

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30 Citations (Scopus)


The sulfated metal oxides (SMOs) sulfated stannia (SnS), sulfated iron oxide (FeS), and sulfated titanium dioxide (TiS) have been synthesized and examined as support materials/cocatalysts/activators for molecule-based olefin polymerization and hydrogenation catalysis. 13C CPMAS NMR spectroscopic analysis of Cp 2Zr( 13CH 3) 2/SMO chemisorption shows that cationic zirconocenium species are formed along with varying amounts of catalytically inactive μ-oxo (Cp 2Zr(CH 3)O-surface) species, depending on the support material. Ethylene polymerization data with the supported catalysts show that polymerization activity is dependent on both precursor ligation [Zr(CH 2Ph) 4 > (Me 5Cp)ZrMe 3] and the nature of the support (SnS > FeS > TiS). Poisoning studies were performed in conjunction with ethylene polymerization, mediated by (Me 5Cp) ZrMe 3 supported on each SMO, and reveal that, for (Me 5Cp)ZrMe 3/SnS, 61 ± 5% of the Zr sites are catalytically significant, while, for (Me 5Cp)ZrMe 3/FeS, this quantity is 22 ± 2%, and for (Me 5Cp)ZrMe 3/TiS, 63 ± 9%. These catalysts are also active for benzene hydrogenation and are separable from liquid-phase products using physical or, in the case of FeS, magnetic techniques.

Original languageEnglish
Pages (from-to)9456-9462
Number of pages7
Issue number22
Publication statusPublished - Oct 26 2004


ASJC Scopus subject areas

  • Materials Science(all)
  • Condensed Matter Physics
  • Surfaces and Interfaces
  • Spectroscopy
  • Electrochemistry

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