One-dimensional metal atom chain [Ru(CO)4]n as a catalyst precursor—Hydroformylation of 1-hexene using carbon dioxide as a reactant

Kontkanen, Maija-Liisa; Oresmaa, Larisa; Moreno, M. Andreina; Jänis, Janne; Laurila, Elina; Haukka, Matti

doi:10.1016/j.apcata.2009.06.006

Cited by 46 publications

(21 citation statements)

References 69 publications

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“…68 However, with the addition of small concentrations of Pd, Ga, Li, K, and Na (depending which catalyst is used) to the catalysts, CO 2 conversion and selectivity to alcohols could be increased. 115,121,122 Nevertheless, direct conversion of CO 2 to ethanol has not been accomplished for a large-scale operation. 115,121,122 Nevertheless, direct conversion of CO 2 to ethanol has not been accomplished for a large-scale operation.…”

Section: Hydrogenation Of Co 2 To Form Fuels or Chemicalsmentioning

confidence: 99%

Carbon cycle in advanced coal chemical engineering

Xie

2015

Chem. Soc. Rev.

157

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This review summarizes how the carbon cycle occurs and how to reduce CO2 emissions in highly efficient carbon utilization from the most abundant carbon source, coal. Nowadays, more and more attention has been paid to CO2 emissions and its myriad of sources. Much research has been undertaken on fossil energy and renewable energy and current existing problems, challenges and opportunities in controlling and reducing CO2 emission with technologies of CO2 capture, utilization, and storage. The coal chemical industry is a crucial area in the (CO2 value chain) Carbon Cycle. The realization of clean and effective conversion of coal resources, improving the utilization and efficiency of resources, whilst reducing CO2 emissions is a key area for further development and investigation by the coal chemical industry. Under a weak carbon mitigation policy, the value and price of products from coal conversion are suggested in the carbon cycle.

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Section: Hydrogenation Of Co 2 To Form Fuels or Chemicalsmentioning

confidence: 99%

Carbon cycle in advanced coal chemical engineering

Xie

2015

Chem. Soc. Rev.

157

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“…Structures that incorporate one-dimensional metal atom chains attract interest for a variety of reasons, such as their conductivity [1,2], luminescence [3][4][5], vapochromism [6][7][8], and magnetic [9][10][11], and catalytical [12][13][14][15] properties. Some of these properties are linked directly to the interacting metal atoms in the metal chain, while others can be attributed to metal-ligand interactions of single units in the chain.…”

Section: Introductionmentioning

confidence: 99%

Metal–metal interactions in linear tri-, penta-, hepta-, and nona-nuclear ruthenium string complexes

2011

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Density functional theory (DFT) methodology was used to examine the structural properties of linear metal string complexes: [Ru(3)(dpa)(4)X(2)] (X = Cl(-), CN(-), NCS(-), dpa = dipyridylamine(-)), [Ru(5)(tpda)(4)Cl(2)], and hypothetical, not yet synthesized complexes [Ru(7)(tpta)(4)Cl(2)] and [Ru(9)(ppta)(4)Cl(2)] (tpda = tri-α-pyridyldiamine(2-), tpta = tetra-α-pyridyltriamine(3-), ppta = penta-α-pyridyltetraamine(4-)). Our specific focus was on the two longest structures and on comparison of the string complexes and unsupported ruthenium backboned chain complexes, which have weaker ruthenium-ruthenium interactions. The electronic structures were studied with the aid of visualized frontier molecular orbitals, and Bader's quantum theory of atoms in molecules (QTAIM) was used to study the interactions between ruthenium atoms. The electron density was found to be highest and distributed most evenly between the ruthenium atoms in the hypothetical [Ru(7)(tpta)(4)Cl(2)] and [Ru(9)(ppta)(4)Cl(2)] string complexes.

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“…[28] This hypothesis was confirmed by the observation that the presence of 3-alkyl-1,2-dimethylimidazolium salts slowed the hydrogenation rates.The potential use of Ru as a hydroformylation catalyst is of interest, as Rh is much less abundant, [7][8][9] and several Ru-catalyzed processes involving hydroformylation/hydrogenation [21][22][23][24][25] and hydroaminomethylation [17] were recently developed. However, a much more interesting system is that which can catalyze cascade reactions (i.e., CO 2 reduction to CO, hydroformylation, and hydrogenation sequence to produce alcohols of high added value).There are reports that this process is viable if either a Ru-based system with LiCl salts dissolved in N-methylpyrrolidone [35][36][37] or a biphasic imidazolium ILs/toluene [38][39][40][41] (Figure 1) system is used. Advances in this area revealed that if the Ru-catalyzed hydroformylation of 1-hexene (using CO 2 as the CO source) was performed by using 1-butyl-3-methylimidazolium chloride [BMI·Cl] salts [42] (30 equiv.…”

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confidence: 99%

Ruthenium‐Catalyzed Hydroformylation of Alkenes by using Carbon Dioxide as the Carbon Monoxide Source in the Presence of Ionic Liquids

et al. 2014

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Dedicated to the memory of Prof. Roberto F. Souza, one of the pioneers of ionic liquid phase organometallic catalysisThe reaction of [BMI·Cl] (BMI = 1-butyl-3-methylimidazolium) or [BMMI·Cl] (BMMI = 3-butyl-1,2-dimethylimidazolium) with Ru 3 (CO) 12 generates Ru-hydride-carbonyl-carbene species in situ that are efficient catalysts for a reverse water gas shift/ hydroformylation/hydrogenation cascade reaction. The addition of H 3 PO 4 increased the catalytic activity of the first step (i.e., the hydrogenation of CO 2 to CO). Under the optimized reaction conditions [120 8C and 6.0 MPa CO 2 /H 2 (1:1) for 17 h], cyclohexene and 2,2-disubstituted alkenes were easily functionalized to alcohols through sequential hydroformylation/carbonyl reduction.Carbon dioxide sequestration and its use as a feedstock in industrial processes are major challenges in the development of alternative greener and sustainable processes. [1] Indeed, several catalytic processes are under investigation, and they include the incorporation of CO 2 through the addition to epoxides to generate organic carbonates, diols, and polycarbonates by using either organic or metal-based catalysts. [2] However, the substitution of carbon monoxide (CO) by carbon dioxide (CO 2 ) in carbonylation reactions [3][4][5][6] may allow for new applications with broader use for this important and abundant but poorly reactive substrate. Indeed, at the industrial scale, the hydroformylation [7,8] of alkenes is one of the most important applications of homogeneous catalysis, and over 9 million tons of socalled oxo products, such as aldehydes and alcohols, are produced each year. [9] Rh-modified systems are the catalysts of choice for this reaction, as they are highly active and selective for the formation of aldehydes, [7,8] as well as for cascade reactions involving hydroformylation/Witting, [10] hydroaminomethylation sequences, [11,12] and hydroformylation/cyclization reactions. [13][14][15][16] Other metals, such as Pt and Ru, have been much less studied owing to their high hydrogenation activity, which results in the formation of large amounts of alkanes as byproducts. [17][18][19][20] However, the use of Rh-Ru bimetallic systems is of interest for the production of alcohols by hydroformylation/hydrogenation se-quences. [21][22][23][24][25] The differences in selectivity could be easily understood if we look at the hydroformylation and hydrogenation mechanisms catalyzed by Rh I and Ru 0 systems, as the active catalytic species under hydroformylation conditions are the RhÀH and the RuÀ(H) 2 species. [7][8][9]26] The accepted mechanism for the formation of MÀ(H) 2 is the homolytic cleavage of the HÀH bond, as the formation of MÀH occurs either by intramolecular (ligands) or intermolecular (external base) heterolysis of the HÀH bond, which favors the formation of MÀH species. [12,27,28] For instance, cationic [RuÀH] + species species are described as the catallytically active species in the Ru-catalyzed hydrogenation of acids, cyclic carbonates, and CO 2 to alcohol. [...

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One-dimensional metal atom chain [Ru(CO)4]n as a catalyst precursor—Hydroformylation of 1-hexene using carbon dioxide as a reactant

Cited by 46 publications

References 69 publications

Carbon cycle in advanced coal chemical engineering

Carbon cycle in advanced coal chemical engineering

Metal–metal interactions in linear tri-, penta-, hepta-, and nona-nuclear ruthenium string complexes

Ruthenium‐Catalyzed Hydroformylation of Alkenes by using Carbon Dioxide as the Carbon Monoxide Source in the Presence of Ionic Liquids

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