Organometallic molecule-support interactions. Highly active organozirconium hydrogenation catalysts and the formation of cationic species on alumina surfaces

Klaus Hermann Dahmen, David Hedden, Robert L. Burwell, Tobin J. Marks

Research output: Contribution to journalArticlepeer-review

76 Scopus citations

Abstract

When supported upon dehydroxylated (DA) or partially dehydroxylated (PDA) alumina, the organozirconium complexes (C5H6)2Zr(CH3)2 (1), [(CH3)5C5]2Zr(CH3)2 (2), and [(CH3)5C5]Zr(CH3)3 (3) are highly active catalysts for propylene hydrogenation. Turnover frequencies (s-1) at -63 °C (DA, PDA) are as follows: for 1, 0.3, 0.1; for 2, 0.2, 0.06; and for 3, 1.1, 0.3. CO poisoning experiments indicate ≲4% of 1/DA and ≲12% of 3/DA Zr sites are catalytically active. Ethylene polymerization activity follows the order 3 ≫ 1≈2, and DA > PDA. Solid-state 13C CPMAS NMR spectra of (C5H5)2Zr(*CH3)2/DA and (C5H5)2Zr- (*CH3)2/PDA (*C = 90% 13C) evidence *CH3 transfer to A1 surface sites and formation, inter alia, of Cp2Zr(*CH3)+ species. Such processes also occur on PDA.

Original languageEnglish (US)
Pages (from-to)1212-1214
Number of pages3
JournalLangmuir
Volume4
Issue number5
DOIs
StatePublished - Sep 1 1988

ASJC Scopus subject areas

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

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