Surface organometallic chemistry has been reviewed with a special focus on environmentally relevant transformations (C–H activation, CO₂conversion, oxidation).

The epoxidation of cyclohexene with aqueous hydrogen peroxide over mesostructured Ti(Cp)₂Cl₂-grafted silica catalysts is described for the first time. Three kinds of Ti-containing systems with different textural properties have been employed: Ti/SiO₂, Ti/MCM-41 and Ti/MCM-48. A minimal local H₂O₂ concentration in the surroundings of Ti sites, obtained by a controlled dropwise addition of aqueous H₂O₂ (4.17 mmol H₂O₂ h⁻¹ g_cat ⁻¹), is crucial for an effective and highly selective epoxidation. Excellent selectivity (>98%) in cyclohexene epoxide is obtained at the end of the slow H₂O₂ addition in acetonitrile. Higher yields in epoxide are found over Ti/MCM-48 than over Ti/MCM-41 or Ti/SiO₂ thanks to better isolation, dispersion and stability of Ti(IV) sites.