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HOMOGENEOUS TRIDENTATE RUTHENIUM BASED HYDROGENATION CATALYSTS FOR THE DEOXYGENATION OF BIOMASS DERIVED SUBSTRATES IN AQUEOUS ACIDIC MEDIA

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dc.contributor.advisor Schlaf, Marcel
dc.contributor.author Oswin, Chris
dc.date.accessioned 2013-08-30T17:24:40Z
dc.date.available 2013-08-30T17:24:40Z
dc.date.copyright 2013-08
dc.date.created 2013-08-01
dc.date.issued 2013-08-30
dc.identifier.uri http://hdl.handle.net/10214/7438
dc.description.abstract Project I: [Ru(OH2)3(4'-phenyl-2,2':6',2''-terpyridine)](OTf)2 as a Homogeneous Hydrogenation Catalyst for Biomass Derived Substrates. The complex [Ru(OH2)3(4'-phenyl-2,2':6',2''-terpyridine)](OTf)2 has been shown to be an active ionic hydrogenation catalyst for selected carbonyls, diols and glycerol by the Schlaf group. It was postulated to also be active for other biomass derived substrates such as levulinic acid (LA), furfural and 5-hydroxymethyl furfural (HMF). Synthesis of the complex was optimized and full characterization carried out by 1H/13C –NMR. The complex was tested against LA in aqueous sulfolane medium and the furfural/HMF model system 2,5-hexanedione in water. Activity of the complex was compared to the analogous metal-ligand bifunctional (MLB) system described in Project II. The complex exhibited good thermal stability up to 200 oC in 90/10 wt% sulfolane/water mixtures and was capable of hydrogenation of LA to γ-valerolactone in 95% yield. Addition of protic acids to the reaction mixture and increasing proportions of water decreased the activity of the complex towards the hydrogenation of LA. Project II: [Ru(OH2)3(di(picolyl)amine)](OTf)2 as an acid-, water- stable, metal-ligand bifunctional deoxygenation catalyst. The complex [Ru(OH2)3(di(picolyl)amine)](OTf)2 was postulated to be an active MLB ionic hydrogenation catalyst under acidic aqueous conditions. Using the substantially labile [Ru(DMF)6](OTF)3 ruthenium complex as the precursor, the desired complex was prepared insitu by coordination of the DPA ligand and concomitant reduction of Ru3+ to Ru2+. The complex was characterized by 1H/13C-NMR and tested for the hydrogenation of LA, 2,5-hexanedione, furfural and HMF under acidic aqueous conditions. The complex exhibited thermal stability up to 150 oC and was active for the hydrogenation of carbonyls, as demonstrated by the conversion of 2,5-hexanedione to 2,5-hexanediol in 94% yield in water. Addition of H3PO4 as an acid cocatalyst resulted in nearly complete conversion to dimethyltetrahydrofuran (DMTHF) but further deoxygenation could not be achieved. Direct comparision of [Ru(OH2)3(di(picolyl)amine)](OTf)2 and [Ru(OH2)3(4'-phenyl-2,2':6',2''-terpyridine)](OTf)2 under identical conditions against LA and 2,5-hexanedione demonstrated that the[Ru(OH2)3(di(picolyl)amine)](OTf)2 catalyst is more active than the [Ru(OH2)3(4'-phenyl-2,2':6',2''-terpyridine)](OTf)2 complex in all cases, suggesting that the di(picolyl)amine complex operates through a MLB ionic hydrogenation mechanism. en_US
dc.description.sponsorship NSERC en_US
dc.language.iso en en_US
dc.rights Attribution-NoDerivs 2.5 Canada *
dc.rights.uri http://creativecommons.org/licenses/by-nd/2.5/ca/ *
dc.subject chemistry en_US
dc.subject ruthenium en_US
dc.subject biomass en_US
dc.subject levulinic acid en_US
dc.subject biofuels en_US
dc.subject deoxygenation en_US
dc.subject furfural en_US
dc.subject hydrogenation en_US
dc.subject fuels en_US
dc.subject alkanes en_US
dc.subject aqueous en_US
dc.title HOMOGENEOUS TRIDENTATE RUTHENIUM BASED HYDROGENATION CATALYSTS FOR THE DEOXYGENATION OF BIOMASS DERIVED SUBSTRATES IN AQUEOUS ACIDIC MEDIA en_US
dc.type Thesis en_US
dc.degree.programme Chemistry en_US
dc.degree.name Master of Science en_US
dc.degree.department Department of Chemistry en_US


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