Cyclopentadienyl–Silsesquioxane Titanium Catalysts: Factors Affecting Their Formation and Activity in Olefin Epoxidation with Aqueous Hydrogen Peroxide

María Ventura, Vanessa Tabernero, Tomás Cuenca, Beatriz Royo Cantabrana, Gerardo Jiménez

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

The reaction of titanium chlorosilyl-substituted cyclopentadienyl (Cp) complexes, Ti(η5-C5H3R′SiMe2Cl)Cl3(R′ = H, 1b; SiMe3, 1c), with 1 equiv. of various silsesquioxane trisilanols, R7Si7O9(OH)3(R = iBu, 2a; Ph, 2b), affords either corner-capped Cp derivatives, Ti(η5-C5H3R′SiMe2Cl)(R7Si7O123O3) (R′ = H, R = iBu, 5a, Ph, 5b; R′ = SiMe3, R = iBu, 7a, Ph, 7b), or cyclopentadienyl–silsesquioxane complexes, Ti(η5-C5H4SiMe2OR7Si7O112O2)Cl (R′ = H, R = iBu, 6a, Ph, 6b; R′ = SiMe3, R = iBu, 8a, Ph, 8b), depending on the reaction conditions. In any case, upon heating, kinetic products 5 and 7 are transformed into the corresponding thermodynamic products 6 and 8, respectively. The electron-donating ability of the Cp ring is a relevant controlling parameter: a strong π-donor character facilitates the isomerization process. In addition, the nature of the silicon substituents in the silsesquioxane framework, the type of solvent, and the reaction temperature are also factors that significantly affect this process. Cyclopentadienyl–silsesquioxane complexes 6b and 8b are efficient and selective catalysts for epoxidation with aqueous hydrogen peroxide under mild conditions. Such a catalytic efficiency is attributed to the hydrophobic environment generated about the titanium atom by the Cp ring incorporated into the cyclopentadienyl–silsesquioxane ligand.

Original languageEnglish
Pages (from-to)2843-2849
Number of pages7
JournalEuropean Journal of Inorganic Chemistry
Volume2016
Issue number17
DOIs
Publication statusPublished - 2016

Keywords

  • Cyclopentadienyl ligands
  • Epoxidation
  • Hydrogen peroxide
  • Titanasilsesquioxane
  • Titanium

Fingerprint Dive into the research topics of 'Cyclopentadienyl–Silsesquioxane Titanium Catalysts: Factors Affecting Their Formation and Activity in Olefin Epoxidation with Aqueous Hydrogen Peroxide'. Together they form a unique fingerprint.

  • Cite this