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

Christopher P. Nicholas; Tobin J. Marks

doi:10.1021/la0492106

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

Christopher P. Nicholas, Tobin J. Marks^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

40 Scopus citations

Abstract

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 language	English (US)
Pages (from-to)	9456-9462
Number of pages	7
Journal	Langmuir
Volume	20
Issue number	22
DOIs	https://doi.org/10.1021/la0492106
State	Published - Oct 26 2004

ASJC Scopus subject areas

General Materials Science
Condensed Matter Physics
Surfaces and Interfaces
Spectroscopy
Electrochemistry

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

abstract = "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.",

author = "Nicholas, {Christopher P.} and Marks, {Tobin J.}",

year = "2004",

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N2 - 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.

AB - 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.

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

Abstract

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