Synthesis of Ruthenium Carbonyl Complexes with Phosphine or Substituted Cp Ligands, and Their Activity in the Catalytic Deoxygenation of 1,2-Propanediol

Ghosh, Prasenjit; Fagan, Paul J.; Marshall, William J.; Hauptman, Elisabeth; Bullock, R. Morris

doi:10.1021/ic900413y

Cited by 39 publications

(30 citation statements)

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“…sulfuric acid) were added to improve catalytic conversions. There are also reports [46][47][48][49][50][51][52] on the use of homogeneous ruthenium catalysts in combination with triflic acid (HOTf) and sulfolane as the solvent for the selective hydrodeoxygenation of a secondary alcohol in the presence of a primary alcohol. For example, Schlaf et al [51] reported the production of 1-propanol from 6 using [{Cp*Ru(CO) 2 While preparing this manuscript, Dumesic et al [44] reported hydrodeoxygenation reactions of various diols and triols using bimetallic Rh-ReO x catalysts on carbon supports.…”

Section: 6-hexanediolmentioning

confidence: 99%

From 5-Hydroxymethylfurfural (HMF) to Polymer Precursors: Catalyst Screening Studies on the Conversion of 1,2,6-hexanetriol to 1,6-hexanediol

et al. 2012

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1,6-hexanediol (1) is an important polymer precursor for the polyester industry. In this paper, exploratory catalyst screening studies on the synthesis of 1 from 1,2,6-hexanetriol (2) are described via two different routes. The latter is available by a two-step procedure from 5-hydroxymethylfurfural (HMF, 3), a promising bio-based platform chemical. In the first approach, the direct catalytic hydrodeoxygenation of 2 to 1 with heterogeneous catalysts and molecular hydrogen was explored. Best results were obtained using a Rh-ReO x /SiO 2 catalyst in water (180°C, 80 bar H 2 , 20 h reaction time), leading to full conversion of 2 and 73 % selectivity to 1, the main byproduct being 1,5-hexanediol (4). In a second approach, 2 was first converted to tetrahydropyran-2-methanol (2-THPM, 5) in quantitative yield using triflic acid as catalyst (125°C, 30 min). Various catalysts were explored for the subsequent ring opening/hydrodeoxygenation of 5 to 1 using a hydrogenation protocol and the best results were obtained with a Rh-ReO x /SiO 2 catalyst, viz. 96 % selectivity to 1 at 26 % conversion (120°C, 80 bar H 2 , 20 h).

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Section: 6-hexanediolmentioning

confidence: 99%

From 5-Hydroxymethylfurfural (HMF) to Polymer Precursors: Catalyst Screening Studies on the Conversion of 1,2,6-hexanetriol to 1,6-hexanediol

et al. 2012

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“…[5,6] To date only a few alcohol-to-olefin dehydration reactions catalyzed by homogeneous catalysts have been reported. Catalysts based on ruthenium [7,8] have proven active in the combined dehydration/hydrogenation of diols, and also palladium- [9] and zinc-based [10] catalysts have been reported for the dehydration of alcohols. A remarkable non-metal-based dehydration of glycerol and erythritol that makes use of formic acid was recently reported by Ellman et al [11] High-valent rhenium complexes have also shown promising activity in dehydration reactions.…”

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confidence: 99%

Catalytic Dehydration of Benzylic Alcohols to Styrenes by Rhenium Complexes

2010

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The catalytic dehydration of (poly)alcohols represents a facile route to (functionalized) olefins. Current dehydration methods use strong acids, such as sulfuric acid or p-toluenesulfonic acid (pTSA), [1] or solid acids, such as zeolites [2] or metal oxides. [3,4] The major problems with these methods are their low selectivity and low functional group tolerance. Therefore a selective, widely useable dehydration method is highly desirable. Such a method might prove useful in the dehydration of biomassbased compounds, which are very rich in hydroxyl groups. Dehydration of both the (hemi)cellulosic components of biomass as well as aromatic lignin components could provide very interesting building blocks for the chemical industry. [5,6] To date only a few alcohol-to-olefin dehydration reactions catalyzed by homogeneous catalysts have been reported. Catalysts based on ruthenium [7,8] have proven active in the combined dehydration/hydrogenation of diols, and also palladium- [9] and zinc-based [10] catalysts have been reported for the dehydration of alcohols. A remarkable non-metal-based dehydration of glycerol and erythritol that makes use of formic acid was recently reported by Ellman et al. [11] High-valent rhenium complexes have also shown promising activity in dehydration reactions. Multiple methods were reported: Methyltrioxorhenium(VII) (MTO; CH 3 ReO 3 ) showed good results at room temperature in the dehydration of various alcohols, [12] while in the presence of hydrogen at higher temperature and pressure epoxides were deoxygenated in good and diols in moderate yield.[13] Cp*ReO 3 performed very well in the presence of PPh 3 in the deoxygenation of various diols and polyols, [14] however, phosphine oxide was obtained as a byproduct in quantitative amounts. Herein, we report on a study into various rhenium-based catalysts for the dehydration of alcohols to olefins under mild conditions. We initially focused on the dehydration of various benzylic alcohols.Following the original procedure by Zhu and Espenson, [12] the first attempts using MTO as a catalyst for the dehydration of 1,2,3,4-tetrahydronaphthol 1 to 1,2-dihydronaphthalene 2 (Scheme 1) at room temperature gave surprisingly poor results. The yield of 2 using benzene as a solvent was only 4 %, while 71 % was originally reported. In our hands, the highest yield of 2 obtained was 10 %, using THF as solvent, a reaction time of 3 days, and 10 mol % MTO as catalyst at room temperature. Using the same procedure at elevated temperature, however, gave very good results. In toluene at 100 8C, complete conversion was obtained after as little as 30 min reaction time, yielding olefin 2 as the single product. Lowering the amount of catalyst to 1 mol % also resulted in complete conversion after 30 min. Next, different commercially available rhenium complexes were tested for their activity in reaction 1. A blank reaction gave low conversion after 3 days of reaction time, yielding a mixture of both olefin and ether. Re 2 (CO) 10 did show some activity, yet poor selectivity...

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“…Therefore over-hydrogenolysis to propanols and even propane can proceed over the catalysts that can work by the dehydration + hydrogenation route. Homogeneous Ru and Ir complexes combined with external acid are typical catalysts for production of propanols or propane from glycerol [10,11] and 1,2-PrD [12][13][14]. In contrast, under more basic conditions over heterogeneous metal catalysts, the dehydrogenation + dehydration + hydrogenation route is preferred to the dehydration + hydrogenation route.…”

Section: Conventional Hydrogenolysis Of Glycerol and Tetrahydrofurfurmentioning

confidence: 99%

Selective Hydrogenolysis of C–O Bonds Using the Interaction of the Catalyst Surface and OH Groups

Tomishige

Nakagawa

Tamura

2014

Topics in Current Chemistry

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Hydrogenolysis of C-O bonds is becoming more and more important for the production of biomass-derived chemicals. Since substrates originated from biomass usually have high oxygen content and various kinds of C-O bonds, selective hydrogenolysis is required. Rhenium or molybdenum oxide modified rhodium and iridium metal catalysts (Rh-ReO(x), Rh-MoO(x), and Ir-ReO(x)) have been reported to be effective for selective hydrogenolysis. This review introduces the catalytic performance and reaction kinetics of Rh-ReO(x), Rh-MoO(x), and Ir-ReO(x) in the hydrogenolysis of various substrates, where selectivity is especially characteristic. Based the model structure of the catalysts and the reaction mechanism, the role of the oxide components is to make the interaction between the OH groups in the substrates and the catalyst surface, and the role of metal components is to dissociate hydrogen molecule heterolytically to give hydride and proton.

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Synthesis of Ruthenium Carbonyl Complexes with Phosphine or Substituted Cp Ligands, and Their Activity in the Catalytic Deoxygenation of 1,2-Propanediol

Cited by 39 publications

References 61 publications

From 5-Hydroxymethylfurfural (HMF) to Polymer Precursors: Catalyst Screening Studies on the Conversion of 1,2,6-hexanetriol to 1,6-hexanediol

From 5-Hydroxymethylfurfural (HMF) to Polymer Precursors: Catalyst Screening Studies on the Conversion of 1,2,6-hexanetriol to 1,6-hexanediol

Catalytic Dehydration of Benzylic Alcohols to Styrenes by Rhenium Complexes

Selective Hydrogenolysis of C–O Bonds Using the Interaction of the Catalyst Surface and OH Groups

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