Heterogeneous and homogeneous hydrogenation catalysts for the selective deoxygenation of biomass feedstocks.

摘要

Project I: Metal-Ligand Bifunctional Homogenous Ionic Hydrogenation by a Ruthenium(II) Complex containing the 6,6'-diamino-2,2 '-bipyridine ligand.;Project II: Activation of316 Stainless Steel as a Catalyst for the Hydrogenation of Biomass-derived Substrates under Acidic Aqueous Conditions.;A series of hydrogenation experiments with glycerol in aqueous acidic medium under reducing conditions (hydrogen pressure) and as a function of temperature and acid concentration demonstrated the ability of these reaction conditions to activate 316SS as a hydrogenation catalyst.;The complexes [Ru(II)(eta5-C5H5)(bipy)(CH 3CN)](OTf) [6], and [Ru(II)(eta5-C 5H5)(dabipy)(CH3CN)](OTf) [7] were postulated to be active hydrogenation catalysts, both complexes were synthesized and fully characterized by 1H/13C NMR, mass spectrometry, and X-ray crystallography. The ability of [7] to operate through a concerted metal ligand bifunctional mechanism was then demonstrated by comparing its activity to that of the analogous non-aminated system [6] using the hydrogenation of various carbonyls under acidic conditions, with the carbonyls as the solvent and substrate (neat).