103500-16-9Relevant academic research and scientific papers
(OTf)2 as a homogeneous catalyst for the hydrogenation of biomass derived 2,5-hexanedione and 2,5-dimethyl-furan in aqueous acidic medium
Latifi, Elnaz,Marchese, Austin D.,Hulls, Margaret C.W.,Soldatov, Dmitriy V.,Schlaf, Marcel
supporting information, p. 4666 - 4679 (2017/10/13)
The complex [Ru(triphos)(CH3CN)3](OTf)2 is an effective catalyst for the hydrogenation of 2,5-hexanedione and 2,5-dimethyl-furan in aqueous acidic medium at temperatures between 150 and 200 °C realizing up to 96% combined yields of 2,5-hexanediol and 2,5-dimethyl-tetrahydrofuran with the product distribution being sensitive to the amount of acid co-catalyst (HOTf) present. For the furan, the reaction pathway is through an acid-catalyzed hydrolysis to the dione rather than direct hydrogenation of the ring. The hydrogenation of the dione shows a first order dependence on hydrogen pressure as determined by direct hydrogen uptake rate measurements at temperature and pressure (1.38-6.90 MPa at 150 °C) and is postulated to operate through a heterolytic activation of hydrogen gas by [Ru(H)x(triphos)(Y)y]n+ (Y = solvent, water, counter ion) species formed in situ by loss and hydrogenation of the nitrile ligands. In water the catalyst is deactivated by dimerization to [Ru2(μ-OH)3(triphos)2](OTf).
METHOD FOR PRODUCING ALCOHOL BY HYDROGENATING LACTONE AND CARBOXYLIC ACID ESTER IN LIQUID PHASE
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Page/Page column 11, (2010/01/29)
Disclosed is a method for producing an alcohol from a lactone or a carboxylic acid ester, which enables to produce an alcohol from a lactone or a carboxylic acid ester under relatively mild conditions with high yield and high catalytic efficiency. This method also enables to produce an optically active alcohol from an optically active lactone or an optically active carboxylic acid ester. Specifically disclosed is a method for producing an alcohol by hydrogen reducing a lactone or a carboxylic acid ester in the presence of a catalyst containing ruthenium and a phosphine compound represented by the following general formula (1): wherein R1 represents a spacer; R2, R3, R4, R5, R6 and R7 independently represent a hydrogen atom, an alkyl group having 1-12 carbon atoms, an aryl group or a heterocyclic group; and R8, R9, R10, R11, R12 and R13 independently represent an alkyl group having 1-12 carbon atoms, an aryl group or a heterocyclic group.
The ruthenium and iridium coordination chemistry of the tripodal ligand CH3C{CH2P(m-CF3-C6H4)2}3
Suelue, Mustafa,Venanzi, Luigi M.
, p. 70 - 79 (2008/10/08)
The ruthenium(II) complexes [Ru(CF3CO2)2(CF3triphos)], [Ru2(μ-Cl)3(CF3triphos)2]Cl, [RuH(CH3CN)2(CF3triphos)](CF3SO3) and (Ru(CH3CN)3(CF3triphos)](CF3SO3)2 (CF3triphos = CH3C{CH2P(m-CF3C6H4)2}3) were prepared and characterized. The iridium complexes [Ir(COD)(CF3triphos)](+), [IrCl(CO)(CF3triphos)], [Ir(CO)2(CF3triphos)](+), [IrCl3(CF3triphos)] and [IrCl3-n(-)(MeCN)n(CF3triphos)](CF3SO3)n (n = 1, 2 and 3) were also prepared and characterized. The coordination chemistries of these two elements withCF3triphos and with the unsubstituted ligand CH3C{CH2P(C6H5)2}3 (Htriph os) are compared. It is shown that, relative to Htriphos, CF3triphos (a)stabilizes the iridium(I) relative to the iridium(III) oxidation state and (b) its cationic complexes are stronger Lewis acids.
Ruthenium(II) solvento complexes containing the tripod-like ligands MeC(CH2EPh2)3 (E = P or As) and their reactions with carbon monoxide. Crystal and molecular structure of [Ru2(μ-Cl)3(MeC(CH2PPh2) 3)2][BPh4]
Rhodes, Larry F.,Sorato, Carla,Venanzi, Luigi M.,Bachechi, Fiorella
, p. 604 - 610 (2008/10/08)
Treatment of [RuCl2(DMSO)4] with tripod [tripod = MeC(CH2EPh2)3, E = P (triphos) or As (triars)] yields [Ru2(μ-Cl)3-(tripod)2]Cl. In the case of triars the mononuclear intermediate [RuCl2(DMSO)(triars)] can be isolated. This condenses to the corresponding trichloro-bridged complex in MeOH. The chloride ligands of [Ru2(μ-Cl)3(tripod)2]Cl can be abstracted by AgCF3SO3 in MeCN to yield [Ru(MeCN)3(tripod)](CF3SO3)2. When the chloride abstraction is carried out in DMSO and above 100 °C, the products are [Ru(DMSO)3(tripod)](CF3SO3)2, whereas if the reaction is carried out below 100 °C, the mixed-solvent complexes [Ru(H2O)(DMSO)2(tripod)](CF3SO 3)2 are obtained. Reaction of the DMSO complexes with carbon monoxide gives the dicarbonyl triflate complexes [Ru(CF3SO3)(CO)2(tripod)](CF3SO 3). The X-ray diffraction study of a crystal of [Ru2(μ-Cl)3(tripod)2][BPh4] (orthorhombic, of space group Pccn and with a = 19.991 (8) A?, b = 18.388 (7) A?, c = 25.510 (10) A?, and Z = 4) is reported.
