Homogeneous catalysis in water Part II. Synthesis and characterization of ruthenium water-soluble complexes

Fache, Eric; Santini, Catherine C.; Senocq, François; Basset, Jean‐Marie

doi:10.1016/0304-5102(92)85010-d

Cited by 67 publications

(28 citation statements)

References 15 publications

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“…Internal hydride migration to the coordinated aldehyde and protonation of the resulting alkoxide complex by water would release the alcohol product while coordination of formate and its decomposition to CO 2 (bicarbonate) within the coordination sphere of Ru(II) would give back the trans-[RuH 2 (H 2 O)(mtppms) 3 ] catalyst. Similar suggestions were already made concerning the mechanism of aldehyde hydrogenation [25,26]. However, several fine details of the mechanism (coordination mode of the aldehyde, the precise steps of formation of Ru(II)-hydrides on the action of formate in aqueous solutions, etc.)…”

Section: Resultssupporting

confidence: 67%

“…In the predominantly aqueous solvents (≤20% (v/v) 2-propanol), the aldehyde substrate does not dissolve completely, while in the ≥80% (v/v) 2-propanol range some of the HCOONa remains undissolved. onaldehyde with several well defined Ru(II)-mtppts complexes in water at 35 • C and 50 bar H 2 pressure [25,26]. In hydrogen transfer from aqueous formate to cinnamaldehyde in the biphasic system studied by us earlier at 80 • C, the highest TOF was 54 h −1 [45].…”

Section: Resultsmentioning

confidence: 89%

“…Solubility of inorganic salts in the aqueous phase can be beneficial, too. For example, significant rate increasing effects of various cations were observed in aqueous-organic biphasic hydrogenation of aldehydes with several Ru(II)-mtppts catalysts [25,26]. Finally, mutual solubility of water in the organic phase and vice versa should also be considered.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Unexpectedly fast catalytic transfer hydrogenation of aldehydes by formate in 2-propanol–water mixtures under mild conditions

Szatmári

Papp²,

Joó

et al. 2015

Catalysis Today

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Unsaturated aldehydes were efficiently reduced by transfer hydrogenation from sodium formate in water-2-propanol mixtures using a water-soluble Ru(II)-tertiary phosphine catalyst. The reaction yielded unsaturated alcohols with complete selectivity and without hydrogenation or isomerization of C C bonds of the substrates. Very high reaction rate was observed in the transfer hydrogenation of cinnamaldehyde already at 30 • C with turnover frequency of 160 h −1 and this increased to 3800 h −1 at 70 • C. Consequently, the method is applicable to the synthesis of unsaturated alcohols in case of heat sensitive or highly volatile aldehydes, too. Based on multinuclear NMR investigations, trans-[RuH 2 (H 2 O)(mtppms) 3 ] is suggested as the key catalytic species.

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Section: Resultssupporting

confidence: 67%

Section: Resultsmentioning

confidence: 89%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Unexpectedly fast catalytic transfer hydrogenation of aldehydes by formate in 2-propanol–water mixtures under mild conditions

Szatmári

Papp²,

Joó

et al. 2015

Catalysis Today

View full text Add to dashboard Cite

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“…The value of the activation energy for the main reaction (Ea 2 ) is close to the value reported by Basset et al (80 kJ/mol) for the hydrogenation of propionaldehyde using a homogeneous Ru-TPPTS complex in water [40].…”

Section: Modeling Resultssupporting

confidence: 67%

Hydrogenation of fast pyrolyis oil and model compounds in a two-phase aqueous organic system using homogeneous ruthenium catalysts

Mahfud

Ghijsen

Heeres

2007

Journal of Molecular Catalysis A: Chemical

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“…Another chlorine-free complex, Ru(H) 2 (TPPTS) 4 , was also prepared from Ru(Cl) 2 (TPP) 3 (Aldrich) according to the literature [22,23]. Ru(Cl) 2 (TPP) 3 was dissolved in THF, an aqueous solution of TPPTS was added to this THF solution, and the mixture was stirred at 60 for 1 h under reflux conditions.…”

Section: Catalyst Preparationmentioning

confidence: 99%

Recyclability of water-soluble ruthenium–phosphine complex catalysts in multiphase selective hydrogenation of cinnamaldehyde using toluene and pressurized carbon dioxide

Fujita

Akihara

Arai

2006

Journal of Molecular Catalysis A: Chemical

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The recyclability of water-soluble ruthenium -phosphine complex catalysts was investigated in water -toluene and in water -pressurized carbon dioxide systems for selective hydrogenation of trans-cinnamaldehyde (CAL). For the first hydrogenation run, the selectivity for cinnamyl alcohol (COL) is high for both toluene and dense CO 2 , because of interfacial catalysis in which the reaction mainly occurs at the interface between the aqueous phase and the other toluene or dense CO 2 phase. The total CAL conversion and the COL selectivity decrease on the second run, more significantly with dense CO 2 than toluene. On the subsequent runs, however, less significant changes were observed. During the first run, the active metal complexes should change to much less active ones such as Ru(H) 2 L n (TPPTS) m (L=COL) by accumulation of the main product of COL. This structural change may occur more easily in multiphase hydrogenation with dense CO 2 than that with toluene, probably because the solubility in the dense CO 2 gas phase is even smaller than that in toluene. For homogeneous reaction of COL in aqueous phase, Ru(H) 2 L n (TPPTS) m catalyzes the isomerization to HCAL compared with the hydrogenation to hydrocinnamyl alcohol. With those complexes, however, the selectivity for COL is still comparable to that for HCAL for multiphase hydrogenation reactions because the hydrogenation of an ampholytic substrate of CAL occurs mainly at interface between water and toluene or dense CO 2 gas phase. Interactions of CO 2 molecules with CAL would also increase the reactivity of carbonyl group of the substrate.

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Homogeneous catalysis in water Part II. Synthesis and characterization of ruthenium water-soluble complexes

Cited by 67 publications

References 15 publications

Unexpectedly fast catalytic transfer hydrogenation of aldehydes by formate in 2-propanol–water mixtures under mild conditions

Unexpectedly fast catalytic transfer hydrogenation of aldehydes by formate in 2-propanol–water mixtures under mild conditions

Hydrogenation of fast pyrolyis oil and model compounds in a two-phase aqueous organic system using homogeneous ruthenium catalysts

Recyclability of water-soluble ruthenium–phosphine complex catalysts in multiphase selective hydrogenation of cinnamaldehyde using toluene and pressurized carbon dioxide

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