103500-17-0Relevant articles and documents
(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).
Synthesis and structural and spectroscopic characterization of new Ru II-dmso precursors with face-capping ligands for use in self-assembly reactions
Iengo, Elisabetta,Zangrando, Ennio,Baiutti, Edi,Munini, Fabio,Alessio, Enzo
, p. 1019 - 1031 (2007/10/03)
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.