Surface Organometallic Chemistry on Metals. Evidence for a New Surface Organometallic Material, Rh[Sn(n-C4H9)x]y/ SiO2, Obtained by Controlled Hydrogenolysis of Sn(n-C4H9)4 on a Rh/SiO2 Catalyst

B. Didillon, C. Houtman, J. P. Candy*, Jean-Marie Maurice Basset, T. Shay

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

64 Scopus citations


Selective hydrogenolysis of Sn(n-C4H9)4 on a Rh/SiO2 catalyst has been carried out at various temperatures and at various coverages of the metallic surface. The surface reaction and the characterization of the grafted organotin complex have been followed by analytical methods, temperature-programmed reaction, electron microscopy, XPS, IR, Mössbauer spectroscopy, 13C CP-MAS solid-state NMR. At room temperature and in the absence of metallic Rh, Sn(n-C4H9)4 is simply physisorbed on the silica surface and can be easily extracted. In the presence of metallic Rh, and provided that the amount of Sn introduced represents less than a monolayer on the metallic surface, the hydrogenolysis of Sn(n-C4H9)4 occurs exclusively on the Rh particle. Only a 13C NMR signal corresponding to ≡SiOSn(n-C4H9)3 was observed on the silica surface when the amount of Sn introduced was higher than ca. one monolayer on the Rh particle. Sn remains on this metallic phase even after hydrogenolysis, as demonstrated by STEM-EDAX experiments. Gas-phase evolution (TPR) and infrared studies show that the hydrogenolysis proceeds by a stepwise cleavage of Sn-alkyl bonds. For low Sn/Rhs ratios (<0.5) the reaction is continuous with formation of surface tin alkyl complexes with various degrees of substitution. For higher Sn/Rhs ratios, there is formation of a well-defined and relatively stable surface organometallic fragment which can be formulated as Rhs[Sn(n-C4H9)2]y. Various possible structures have been proposed, taking into account the various results. Whereas Rhs[Sn(n-C4H9)2]y is the simplest possible model for this stable surface organometallic fragment, the results of molecular modeling seem to rule out such a model (at least at high coverages) on the basis of steric constraints. Another model, which apparently fits the experimental results better, corresponds to the general formula (Rhs)2Sn[Sn(n-C4H9)3]2.

Original languageEnglish (US)
Pages (from-to)9380-9388
Number of pages9
JournalJournal of the American Chemical Society
Issue number21
StatePublished - Oct 1 1993

ASJC Scopus subject areas

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


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