The dimeric ruthenium complex [Cp^RuCl2](2) is easily accessible in a one-pot reaction from RuCl3(solv)(n) and tert-butylacetylene. It features sterically very demanding Cp-roof ligands (Cp^ = eta(5)-1-methoxy-2,4-tert-butyl-3-neopentylcyclopentadienyl), which impart a unique reactivity. Herein we describe the synthesis and the characterization of novel Cp boolean AND Ru complexes bearing a bridging carbene ligand, a linear imido ligand, or an orthometalated phosphine ligand. Furthermore, the microwave-assisted syntheses of the bimetallic complexes [Cp^Ru(mu-Cl)(3)Ru(p-cymene)] and [Cp^Ru(mu-Cl)(3)RhCp*] are described.

The dimeric ruthenium complex [Cp boolean AND RuCl2](2) is easily accessible in a one-pot reaction from RuCl3(solv)(n) and tert-butylacetylene. It features sterically very demanding "Cp-roof" ligands (Cp boolean AND = eta(5)-1-methoxy-2,4-tert-butyl-3-neopentylcyclopentadienyl), which impart a unique reactivity. Herein we describe the synthesis and the characterization of novel Cp boolean AND Ru complexes bearing a bridging carbene ligand, a linear imido ligand, or an orthometalated phosphine ligand. Furthermore, the microwave-assisted syntheses of the bimetallic complexes [Cp boolean AND Ru(mu-Cl)(3)Ru(p-cymene)] and [Cp boolean AND Ru(mu-Cl)(3)RhCp*] are described.

The dinuclear complexes [(p-cymene)RuCl2](2) and [(cyclopentadienyl)MCl2](2) (M = Ru, Rh, Ir) are important starting materials in organometallic chemistry. The standard synthesis of these complexes involves heating of an alcoholic solution of Ru-III, Rh-III, or Ir-III salts with precursors of the -ligands for several hours under reflux. Microwave heating allows these complexes to be obtained within a few minutes without compromising the yields. Furthermore, the microwave-assisted syntheses require less solvent and, in some cases, lower amounts of ligand precursors.

The synthesis and in vitro cytotoxicity of a series of RuII(arene) complexes with carbohydrate-derived phosphite ligands and various arene co-ligands is described. The arene ligand has a strong influence on the in vitro anticancer activity of this series of compounds, which correlates fairly well with cellular accumulation. The most lipophilic compound bearing a biphenyl moiety and a cyclohexylidene-protected carbohydrate is the most cytotoxic with unprecedented IC50 values for the compound class in three human cancer cell lines. This compound shows reactivity to the DNA model nucleobase 9-ethylguanine, but does not alter the secondary structure of plasmid DNA indicating that other biological targets are responsible for its cytotoxic effect.

In an approach to design selectives olid catalysts we start fromt he knowledge,atthe molecularlevel,ofthe reactiontobecatalyzed.Thenhypothesisa re made on then atureo ft he actives itesr equired.A tt hisp oint we are readytosynthesizesolid materials, in where therequiredactivesitesare introduced as well definedentities.On topofthatthe adsorption propertiesof thesolid are taylored to optimizethe interactions between reactants, catalyst andproducts.Following this methodologyw ill presents olid catalysts in where thea ctive sitescorrespondtowelldefinedtransitionmetal complexesand organocatalysts thata re either graftedo rs tructurally builded into solids.In this case, ther oleo ft he solid can go beyond as imple support, since it is designed to interveneinthe reactioneither by stabilizing transitionstatesorbyintroducingadditionalactivesites.Well definedsingleormultiple activesitescan also be introduced into crystallinen anoporous materialsw ith controlleda dsorptionp roperties, andt his allows to perform newacidand redox,one step or multistepreactions.Finallyw ill show that by depositingm etal nanoparticles( Au, Pd,P t) on proactivesupports(CeO 2 ,Fe 2 O 3 , MgO,hydrotalcites,etc.) we can open new catalytic reactionroutesf or C-Cbond formation, oxidations andreductions.These catalytic system allowt he design of multifunctionals olid catalysts, that are able to carryo ut multistepp rocess through cascadet yper eactions that were not possiblebefore.

AbstractIt provides a new approach to trifluoromethylated cyclopropanes.

Anthracene derivatives of ruthenium(II) arene compounds with 1,3,5-triaza-7-phosphatricyclo[3.3.1.1]decane (pta) or a sugar phosphite ligand, viz., 3,5,6-bicyclophosphite-1,2-O-isopropylidene-α-d-glucofuranoside, were prepared in order to evaluate their anticancer properties compared to the parent compounds and to use them as models for intracellular visualization by fluorescence microscopy. Similar IC50 values were obtained in cell proliferation assays, and similar levels of uptake and accumulation were also established. The X-ray structure of [{Ru(η6-C6H5CH2NHCO-anthracene)Cl2(pta)] is also reported.

A two-step process for the synthesis of trifluoromethyl-substituted cyclopropanes is described. Halothane, an anesthetic agent, is added to olefins in a ruthenium-catalyzed Kharasch reaction. The resulting 1,3-dihalides are converted into cyclopropanes by dehalogenation with magnesium. This procedure represents an alternative to metal-catalyzed cyclopropanations involving trifluoromethyl diazomethane.

The cyclopentadienyl Ru complexes Cp*RuCl-(cod) (cod = 1,5-cyclooctadiene), Cp*RuCl(PPh3)(2), and [Cp boolean AND RuCl2](2) (Cp boolean AND = eta(5)-1-methoxy-2,4-di-tert-butyl-3-neo-pentylcyclopentadienyl) are able to catalyze the decomposition of benzyl azides to give 1,3,5-triphenyl-2,4-diazapenta-1,4-diene ("hydrobenzamide"), benzyl-benzylideneamine, and benzonitrile. Reactions with the catalyst precursor [Cp boolean AND RuCl2](2) are particularly fast and give hydrobenzamide with high selectivity. A similar coupling reaction is observed for other benzylic azides but not for (2-azidoethyl)benzene and ethyl-4-azidobutanoate. If the reactions are performed in the presence of water, benzylic azides are converted into aldehydes. Mononuclear tetrazene complexes are formed in stoichiometric reactions of [Cp boolean AND RuCl2](2) with benzyl azide and (2-azidoethyl)benzene.