Hydrogenation and hydrogenolysis of furfural and furfuryl alcohol catalyzed by ruthenium(II) bis(diimine) complexes
نویسندگان
چکیده
The catalytic activity of ruthenium(II) bis(diimine) complexes cis-[Ru(6,6′-Cl2bpy)2(OH2)2](Z)2 (1, Z=CF3SO3; 2, Z= (3,5-(CF3)2C6H3)4B, i.e. BArF) and cis-[Ru(4,4′-Cl2bpy)2(OH2)2](Z)2 (3, Z=CF3SO3; 4, Z=BArF) for the hydrogenation and/or the hydrogenolysis of furfural (FFR) and furfuryl alcohol (FFA) was investigated. Themolecular structures of cis-[Ru(4,4′-Cl2bpy)2(CH3CN)2](CF3SO3)2 (3′) and dimeric cis-[(Ru(4,4′-Cl2bpy)2Cl)2](BArF)2 (5) were characterized by X-ray crystallography. The structures are consistent with the anticipated reduction in steric hindrance about the ruthenium centers in comparison with corresponding complexes containing 6,6′-Cl2bpy ligands.While compounds 1–4 are all active and highly selective catalysts for the hydrogenation of FFR to FFA undermodest reaction conditions, 3 and 4 showed decreased activity. This is best explained in terms of reduced Lewis acidity of the Ru centers and reduced steric hindrance about the metal centers of catalysts 3 and 4. cis-[Ru(6,6′-Cl2bpy)2(OH2)2](BArF)2 (2) also displayed high catalytic efficiency for the hydrogenation of FFA to tetrahydrofurfuryl alcohol. Presumably, this is because coordination of C=C bonds of FFA to the ruthenium center is poorly inhibited by non-coordinating BArF counterions. Interestingly, cis-[Ru(6,6′-Cl2bpy)2(OH2)2] (CF3SO3)2 (1) showed some catalytic activity in ethanol for the hydrogenolysis of FFA to 2-methylfuran, albeit with fairly modest selectivity. Nonetheless, these results indicate that ruthenium(II) bis(diimine) complexes need to be further explored as catalysts for the hydrogenolysis of C-O bonds of FFR, FFA, and related compounds. Copyright © 2012 John Wiley & Sons, Ltd.
منابع مشابه
Supported Metal Catalysts for Total Hydrogenation of Furfural and 5-Hydroxymethylfurfural
The use of biomass-derived compounds as substitutes of pet roleum has received much a t tent ion1)~4). Because of the complex nature of biomass, the conversions of biomass to chemicals usually start with the production of small molecules called platform chemicals by thermal, chemical or biological processing5). Among these platform chemicals, furfural6) and 5hydroxymethylfurfural (HMF)7) are es...
متن کاملHydroconversion of Furfural over Cu-Cr/SiO2 Nanocatalysts: A Comparative Study
Furfural is one of the most promising chemical platforms with bright perspective with respect to the production of biobased chemicals and fuels from lignocellulosic material. Globally, the majority of this biomass derived chemical is converted into furfuryl alcohol, a building block in polymers industry. The vapor-phase hydrogenation of furfural over copper species dispersed on two types of sil...
متن کاملEffect of Calcination Rate on Performance of Co-precipitated Cu-MgO Catalyst in Hydrogenation of Furfural
Co-precipitated Cu-MgO catalysts were prepared and evaluated for the gas-phase hydrogenation of furfural. The effect of heating rate at the calcination step was studied by comparing the performance of three catalysts prepared via the same procedure but calcined at different heating rates. The results established that altering the heating rate could influence the structural properties of the cat...
متن کاملCatalytic Hydrogenation and Hydrodeoxygenation of Furfural over Pt(111): A Model System for the Rational Design and Operation of Practical Biomass Conversion Catalysts
Furfural is a key bioderived platform chemical whose reactivity under hydrogen atmospheres affords diverse chemical intermediates. Here, temperature-programmed reaction spectrometry and complementary scanning tunneling microscopy (STM) are employed to investigate furfural adsorption and reactivity over a Pt(111) model catalyst. Furfural decarbonylation to furan is highly sensitive to reaction c...
متن کاملEnhancement of enantioselectivity by alcohol additives in asymmetric hydrogenation with bis(oxazolinyl)phenyl ruthenium catalysts.
Bis(oxazolinyl)phenyl ruthenium(II) complexes were found to catalyze asymmetric hydrogenation of ketones, in which chiral bulky alcohol additives showed significant enhancement of enantioselectivity even in protic solvents.
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
عنوان ژورنال:
دوره شماره
صفحات -
تاریخ انتشار 2013