title: High-surface-area TiO2 and TiN as catalysts for the C-C coupling of alcohols and ketones.
abstract: To design more sustainable processes for the alkylation of ketones, the use of both atom-ineffective leaving groups such as halides and boron as well as noble-metal-based catalysts should be avoided. For that purpose, high-surface-area titanium nitride was prepared from high-surface-area titanium dioxide using cyanamide as a transcription agent. The resulting nitride as well as the initial oxide proved to be effective and versatile catalysts for the alkylation of ketones with alcohols. Interestingly, the TiN catalyst yields unsaturated compounds, while the oxide-based catalyst mainly yields saturated coupling products. As a result of its metallic properties, TiN shows a strong tendency to catalyse the dehydrogenation of alcohols, which then undergo aldol condensation with ketones. In contrast, TiO(2) promotes the direct nucleophilic attack of ketones on alcohols.
authors.affiliation: Colloid Chemistry Department, Max-Planck Institute of Colloids and Interfaces, Research Campus Golm, 14542 Potsdam, Germany.
authors.forename: Anna
authors.initials: A
authors.lastname: Fischer
authors.forename: Philippe
authors.initials: P
authors.lastname: Makowski
authors.forename: Jens-Oliver
authors.initials: JO
authors.lastname: Müller
authors.forename: Markus
authors.initials: M
authors.lastname: Antonietti
authors.forename: Arne
authors.initials: A
authors.lastname: Thomas
authors.forename: Frederic
authors.initials: F
authors.lastname: Goettmann
mesh_terms: D000438:Alcohols / Q000737:chemistry*; D000478:Alkylation; D002244:Carbon / Q000737:chemistry*; D002384:Catalysis; D007659:Ketones / Q000737:chemistry*; D046529:Microscopy, Electron, Transmission; D015394:Molecular Structure; D009584:Nitrogen / Q000737:chemistry; D016062:Porosity; D013499:Surface Properties; D014025:Titanium / Q000737:chemistry*; D014961:X-Ray Diffraction
chemical_list: D000438:Alcohols; D007659:Ketones; C009495:titanium dioxide; D002244:Carbon; D014025:Titanium; D009584:Nitrogen