112220-35-6Relevant academic research and scientific papers
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 (2005)
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.
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.
