Surface supported metal cluster carbonyls. Chemisorption decomposition and reactivity of Rh4(CO)12 supported on silica and alumina

A. Theolier*, A. K. Smith, M. Leconte, Jean-Marie Maurice Basset, G. M. Zanderighi, R. Psaro, R. Ugo

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

121 Scopus citations

Abstract

Chemisorption of Rh4(CO)12 on to a highly divided silica (Aerosil "0" from Degussa), Leads to the transformation: 3 Rh4(CO)12 → 2 Rh6(CO)16 + 4 CO. Such an easy rearrangement of the cluster cage implies mobility of zerovalent rhodium carbonyl fragments on the surface. Carbon monoxide is a very efficient inhibitor of this reaction, and Rh4(CO)12 is stable as such on silica under a CO atmosphere. Both Rh4(CO)12 and Rh6(CO)16 are easily decomposed to small metal particles of higher nuclearity under a water atmosphere and to rhodium(I) dicarbonyl species under oxygen. From the RhI(CO)2 species it is possible to regenate first Rh4(CO)12 and then Rh6(CO)16 by treatment with CO (Pco ≥ 200 mm Hg) and H2O (PH2O ≥ 18 mm Hg). The reduction of RhI(CO)2 surface species by water requires a nucleophilic attack to produce an hypothetical [Rh(CO)n]m species which can polymerize to small Rh4 or Rh6 clusters in the presence of CO but which in the absence of CO lead to metal particles of higher nuclearity. Similar results are obtained on alumina.

Original languageEnglish (US)
Pages (from-to)415-424
Number of pages10
JournalJournal of Organometallic Chemistry
Volume191
Issue number2
DOIs
StatePublished - Jun 3 1980

ASJC Scopus subject areas

  • Biochemistry
  • Chemical Engineering (miscellaneous)
  • Inorganic Chemistry
  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Science (miscellaneous)
  • Materials Chemistry

Fingerprint Dive into the research topics of 'Surface supported metal cluster carbonyls. Chemisorption decomposition and reactivity of Rh4(CO)12 supported on silica and alumina'. Together they form a unique fingerprint.

Cite this