Surface Organometallic Chemistry: Formation of HFe 3 (CO) 11 from Fe 3 (CO) 12 and Fe(CO) 5 on Silica, Alumina, Magnesia, and Zinc Oxide

F. Hugues, Jean-Marie Maurice Basset*, Y. Ben Taarit, A. Choplin, M. Primet, D. Rojas, A. K. Smith

*Corresponding author for this work

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97 Scopus citations

Abstract

This paper describes, at a molecular level, the organometallic chemistry that occurs during the adsorption of Fe 3 (CO) 12 and Fe(CO) 5 on silica, alumina, magnesia, and zinc oxide. Fe(CO) 5 and Fe 3 (CO) 12 are only weakly adsorbed on silica. In contrast on alumina, magnesia, and zinc oxide there is formation of the anionic hydride HFe 3 (CO) 11 M + (M = Al, Mg, Zn), which has been characterized in the adsorbed state by infrared, UV, and 1 H NMR spectroscopy and which has been extracted from the surface by ion exchange with Et 4 NCl. The results indicate that the surface hydroxyl group of alumina, magnesia, or zinc oxide can make a nucleophilic attack at the coordinated CO as it occurs in solution with formation of the stable surface hydrido cluster. The result is also the first example of a grafted cluster where the grafting occurs by ionic interaction with a surface cation of the oxide lattice. It is possible that the anionic cluster interacts with such a surface cation via the oxygen lone pair of the bridging carbonyl ligand.

Original languageEnglish (US)
Pages (from-to)7020-7024
Number of pages5
JournalJournal of the American Chemical Society
Volume104
Issue number25
DOIs
StatePublished - Jan 1 1982

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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