- (OTf)2 as a homogeneous catalyst for the hydrogenation of biomass derived 2,5-hexanedione and 2,5-dimethyl-furan in aqueous acidic medium
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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).
- Latifi, Elnaz,Marchese, Austin D.,Hulls, Margaret C.W.,Soldatov, Dmitriy V.,Schlaf, Marcel
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supporting information
p. 4666 - 4679
(2017/10/13)
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- METHOD FOR PRODUCING ALCOHOL BY HYDROGENATING LACTONE AND CARBOXYLIC ACID ESTER IN LIQUID PHASE
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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.
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Page/Page column 11
(2010/01/29)
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- Synthesis and structural and spectroscopic characterization of new Ru II-dmso precursors with face-capping ligands for use in self-assembly reactions
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The aim of this work is the preparation of new, easy-to-make, octahedral RuII precursors with facial geometry to be used in self-assembly reactions. We chose dmso as a leaving group and 1,4,7-trithiacyclononane ([9]aneS3), tris(pyrazolyl)methane [CH(pz)3, pz = pyrazol-1-yl], or triphos [CH3C(CH2-PPh2) 3] as the face-capping ligand (fcl). We describe here the preparation and structural characterization of three new dicationic RuII complexes (as triflate salts) of the type fac-[Ru(fcl)(solv)3] 2+, namely fac-[Ru([9]aneS3)(dmso-O)(dmso-S) 2]2+ (3b), which equilibrates in solution with the linkage isomer fac-[Ru([9]aneS3)(dmso-O)2(dmso-S)]2+ (3a), fac-[Ru{CH(pz)3}(dmso-O)(dmso-S)2]2+ (7), and fac-[Ru(triphos)(dmso-O)2(H2O)]2+ (9). In all cases the preferred synthetic procedure involved coordination of the face-capping ligand to cis-[RuCl2(dmso)4] first, followed by replacement of the chlorides with dmso (or water) molecules assisted by addition of AgCF3SO3 (AgOTf). NMR investigations showed that hydrolysis of the dmso ligands occurs very easily for 3 in water and for 9 in chloroform, while for complex 7 only the O-bound dmso ligand is replaced in water. In the course of this work, the following complexes were also isolated and structurally characterized: fac-[Ru([9]aneS3)Cl(dmso-S) 2][OTf] (2), trans,cis,cis-[RuCl2(dmso-S) 2{CH(pz)2(pz)}] (4), trans,cis,cis-[RuCl 2(dmso-S)2(pzH)2] (5), fac-[Ru{CH(pz) 3}Cl2(dmso-S)] (6), fac-[Ru([9]aneS3)(py) 3][OTf]2 (11), fac-[Ru([9]aneS3)(py) 2-(CH3CN)][OTf]2 (13), and fac-[Ru([9]aneS 3O)(dmso-O)2(dmso-S)][OTf]2 ([9]aneS 3O = 1,4,7-trithiacyclononane 1-oxide); in 4 the tripodal tris(pyrazolyl)methane acts as a bidentate ligand. Wiley-VCH Verlag GmbH & Co. KGaA, 2005.
- Iengo, Elisabetta,Zangrando, Ennio,Baiutti, Edi,Munini, Fabio,Alessio, Enzo
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p. 1019 - 1031
(2007/10/03)
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- 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]
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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.
- Rhodes, Larry F.,Sorato, Carla,Venanzi, Luigi M.,Bachechi, Fiorella
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p. 604 - 610
(2008/10/08)
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