A facile route to ruthenium–carbene complexes and their application in furfural hydrogenation

Strassberger, Zea; Mooijman, M.; Ruijter, Eelco; Alberts, Albert H.; Graaff, Corien de; Orru, Romano V. A.; Rothenberg, Gadi

doi:10.1002/aoc.1584

Cited by 44 publications

(17 citation statements)

References 23 publications

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“…Recently furfural has been hydrogenated to furfuryl alcohol in water, under very mild reaction conditions, by using polymer stabilized Ru(0) nanoparticles in the presence of cyclodextrins [39]. To our knowledge, only few examples of hydrogenation of FAL to FOL catalyzed by homogeneous metal complexes are reported in the literature [40][41][42][43] but none of them describes the use of rhodium compounds. First, FAL (V) was hydrogenated in sole water as reaction solvent but after 6 h at 60 • C and 2 MPa of H 2 by using a substrate/Rh molar ratio 500/1 conversion to furfuryl alcohol (VI) was only 38% (run 1, Table 3) (Scheme 2).…”

Section: Scheme 1 Hydrogenation Of 2-cyclohexen-1-one (I)mentioning

confidence: 99%

“…Also ruthenium(II)-bis(diimine) complexes are very active and selective in the hydrogenation of FAL to FOL in EtOH at 90-130 • C and 1-5 MPa of hydrogen pressure with the catalyst ranging from 0.4 to 1 mol% [42]. Very interestingly, ruthenium-carbene complexes selectively reduces FAL to FOL by transfer hydrogenation at 60 • C in 24 h but, in this case, the H-donor i-propanol inevitably produces acetone as by-product [43]. At the light of these results we can assert that not only Rh(DHTANa) is active in the green solvent water but it is able to hydrogenate FAL to FOL at mild reaction conditions and by using a rather low substrate/Rh molar ratio (500/1).…”

Section: Scheme 1 Hydrogenation Of 2-cyclohexen-1-one (I)mentioning

confidence: 99%

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Aqueous-phase hydrogenation and hydroformylation reactions catalyzed by a new water-soluble [rhodium]–thioligand complex

Paganelli

Piccolo²,

Pontini

et al. 2015

Catalysis Today

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a b s t r a c tRh(DHTANa) is a new water-soluble catalyst easily obtained by mixing in water the catalytic precursor [Rh(COD)Cl] 2 and the dihydrothioctic acid sodium salt (DHTANa). This catalyst showed to be very active in the hydrogenation of unsaturated substrates as 2-cyclohexen-1-one, the biomass-derived furfural and acetophenone. In this last case the catalytic system obtained by using as water-soluble ligand (R)-(DHTANa) afforded (R)-1-phenylethanol with very modest enantioselectivity. Rh(DHTANa) was active also in the aqueous biphase hydroformylation of styrene producing exclusively the two corresponding aldehydes with 80-86% selectivity toward the branched aldehyde 2-phenylpropanal. This new catalytic system was easily recycled in both hydrogenation and hydroformylation processes and no leaching phenomenon was observed.

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Section: Scheme 1 Hydrogenation Of 2-cyclohexen-1-one (I)mentioning

confidence: 99%

Section: Scheme 1 Hydrogenation Of 2-cyclohexen-1-one (I)mentioning

confidence: 99%

Aqueous-phase hydrogenation and hydroformylation reactions catalyzed by a new water-soluble [rhodium]–thioligand complex

Paganelli

Piccolo²,

Pontini

et al. 2015

Catalysis Today

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“…Thus there is a current need for the development of soluble catalysts for FFR hydrogenation or hydrogenolysis in order to gain a better understanding of the reaction mechanism(s) and the origin of by‐products, as well as to ultimately obtain catalysts that display high activity and product selectivity. In this context, homogeneous ruthenium‐based catalysts, such as ruthenium–carbene complexes and RuCl 2 (PPh 3 ) 3 , have recently been reported to be active for FFR hydrogenation.…”

Section: Introductionmentioning

confidence: 99%

Hydrogenation and hydrogenolysis of furfural and furfuryl alcohol catalyzed by ruthenium(II) bis(diimine) complexes

Gowda

Parkin

Ladipo

2012

Applied Organom Chemis

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The catalytic activity of ruthenium(II) bis(diimine) complexes cis-[Ru(6,6′-Cl 2 bpy) 2 (OH 2 ) 2 ](Z) 2 (1, Z = CF 3 SO 3 ; 2, Z = (3,5-(CF 3 ) 2 C 6 H 3 ) 4 B, i.e. BArF) and cis-[Ru(4,4′-Cl 2 bpy) 2 (OH 2 ) 2 ](Z) 2 (3, Z = CF 3 SO 3 ; 4, Z = BArF) for the hydrogenation and/or the hydrogenolysis of furfural (FFR) and furfuryl alcohol (FFA) was investigated. The molecular structures of cis-[Ru(4,4′-Cl 2 bpy) 2 (CH 3 CN) 2 ](CF 3 SO 3 ) 2 (3′) and dimeric cis-[(Ru(4,4′-Cl 2 bpy) 2 Cl) 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′-Cl 2 bpy ligands. While compounds 1-4 are all active and highly selective catalysts for the hydrogenation of FFR to FFA under modest reaction conditions, 3 and 4 showed decreased activity. This is best explained in terms of reduced Lewis acidity of the Ru 2+ centers and reduced steric hindrance about the metal centers of catalysts 3 and 4. cis-[Ru(6,6′-Cl 2 bpy) 2 (OH 2 ) 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′-Cl 2 bpy) 2 (OH 2 ) 2 ] (CF 3 SO 3 ) 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.

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“…In the past, the Cu-Cr based catalysts were frequently used in industry, but Cr had great impact on the environmental pollution, limiting the further application8. Moreover, the liquid-phase hydrogenation reaction always processed in organic solvents, such as 2-propanol510, octane6, methanol7 and tetrahydrofuran11. The direct discharge of organic solvents would cause severe harm to both human bodies and environment.…”

mentioning

confidence: 99%

Highly selective hydrogenation of furfural to furfuryl alcohol over Pt nanoparticles supported on g-C3N4 nanosheets catalysts in water

Chen

Zhang

et al. 2016

Sci Rep

157

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Graphitic carbon nitride nanosheets were investigated for developing effective Pt catalyst supports for selective hydrogenation of furfural to furfuryl alcohol in water. The nanosheets with an average thickness of about 3 nm were synthesized by a simple and green method through thermal oxidation etching of bulk g-C3N4 in air. Combined with the unique feature of nitrogen richness and locally conjugated structure, the g-C3N4 nanosheets with a high surface area of 142 m2 g−1 were demonstrated to be an excellent supports for loading small-size Pt nanoparticles. Superior furfural hydrogenation activity in water with complete conversion of furfural and high selectivity of furfuryl alcohol (>99%) was observed for g-C3N4 nanosheets supported Pt catalysts. The large specific surface area, uniform dispersion of Pt nanoparticles and the stronger furfural adsorption ability of nanosheets contributed to the considerable catalytic performance. The reusability tests showed that the novel Pt catalyst could maintain high activity and stability in the furfural hydrogenation reaction.

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A facile route to ruthenium–carbene complexes and their application in furfural hydrogenation

Cited by 44 publications

References 23 publications

Aqueous-phase hydrogenation and hydroformylation reactions catalyzed by a new water-soluble [rhodium]–thioligand complex

Aqueous-phase hydrogenation and hydroformylation reactions catalyzed by a new water-soluble [rhodium]–thioligand complex

Hydrogenation and hydrogenolysis of furfural and furfuryl alcohol catalyzed by ruthenium(II) bis(diimine) complexes

Highly selective hydrogenation of furfural to furfuryl alcohol over Pt nanoparticles supported on g-C3N4 nanosheets catalysts in water

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