Surface organometallic chemistry on metals: Controlled hydrogenolysis of Me4Sn, Me3SnR, Me2SnR2, MeSnBu 3 and SnBu4 (R = methyl, n-butyl, tert-butyl, neopentyl, cyclohexyl) onto metallic rhodium supported on silica

Mostafa Taoufik, Marie Anne Cordonnier, Catherine C. Santini*, Jean Marie Basset, Jean Pierre Candy

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

10 Scopus citations

Abstract

The controlled hydrogenolysis of MexSnR4-x (0 ≤ x ≤ 4; R = methyl, n-butyl, tert-butyl, neopentyl, cyclohexyl) onto Rh/SiO 2 is followed by quantitative and qualitative analysis of evolved gases. Only MeH and RH are detected in the evolved gases. There is hydrogenolysis of the Sn-C bonds without any C-C bond hydrogenolysis, leading to formation of grafted organometallic fragments. Using various organotin compounds, MexSnR4-x, it has been possible to determine the regioselectivity of the hydrogenolysis of the Sn-C bonds. The initial selectivity is inversely proportional to the steric bulk of the alkyl group: tBu < Np < Bu. The formation of a five-coordinate tetraalkyl tin on the surface, Rh-SnMexR4-x (symmetry D3h), in which the bulkiest group, e.g., R, is away from the surface could explain these results. This surface five-coordinate tin species could eliminate an alkyl group, generally a methyl group, thus decreasing the steric bulk around the tin, into the equatorial plane of D3h, via a concerted hydrogen transfer-elimination mechanism to give Rh-SnMex-1R4-x. Then, in the successive steps of the hydrogenolysis, the bulkiest group, R, would be eliminated.

Original languageEnglish (US)
Pages (from-to)1531-1537
Number of pages7
JournalNew Journal of Chemistry
Volume28
Issue number12
DOIs
StatePublished - Dec 2004
Externally publishedYes

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Materials Chemistry

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