Triaqua(benzene)ruthenium(II) and triaqua(benzene)osmium(II): synthesis, molecular structure, and water-exchange kinetics

Stebler-Roethlisberger, Monika; Hummel, W.; Pittet, Pierre André; Buergi, H. B.; Lüdi, A.; Merbach, André E.

doi:10.1021/ic00281a009

Cited by 117 publications

(114 citation statements)

References 3 publications

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“…Synthetic sodium hectorite (1) , which has been isolated as the sulfate and structurally characterized [24], is the major species present in the hydrolytic mixture over the pH range from 5 to 8 according to the NMR spectrum. When the yellow solution obtained from dissolving the dinuclear complex [(C 6 H 6 )RuCl 2 ] 2 in water after adjusting the pH to 8 by NaOH is added to white sodium hectorite (1) (corresponding to 75% of the experimentally determined [21] cation exchange capacity of 1), and the presence of metallic ruthenium was proven by its typical reflections in the X-ray diffraction pattern.…”

Section: Resultsmentioning

confidence: 99%

Highly selective low-temperature hydrogenation of furfuryl alcohol to tetrahydrofurfuryl alcohol catalysed by hectorite-supported ruthenium nanoparticles

Khan¹,

Vallat²,

Süß‐Fink³

2011

Catalysis Communications

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a b s t r a c t KeywordsRuthenium nanoparticles Ruthenium-modified hectorite Furfuryl alcohol hydrogenation Metallic ruthenium nanoparticles intercalated in hectorite (particle size~4 nm) were found to catalyse the hydrogenation of furfuryl acohol to give tetrahydrofurfuryl alcohol in methanolic solution under mild conditions. The best results were obtained at 40°C under a hydrogen pressure of 20 bar (conversion 100%, selectivity N 99%). After a total turnover number of 1423, the hectorite supported ruthenium nanoparticles are deactivated but can be recycled and regenerated.

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Section: Resultsmentioning

confidence: 99%

Highly selective low-temperature hydrogenation of furfuryl alcohol to tetrahydrofurfuryl alcohol catalysed by hectorite-supported ruthenium nanoparticles

Khan¹,

Vallat²,

Süß‐Fink³

2011

Catalysis Communications

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“…Also, this class of strong -acid ligands is able to accept electron density from the central Ru II giving rise to a higher charge on the metal, so that Ru II in {( 6 -arene)Ru II } 2ϩ behaves more like a Ru III center (18,35). Acidic hydrolysis of Ru III complexes such as [Ru(NH 3 ) 4 X 2 ] ϩ and [Ru(NH 3 ) 5 X] 2ϩ (X ϭ Cl, Br, and I) occurs via an S N 2 associative pathway (36) in which bond-making is more important than bond-breaking.…”

Section: Discussionmentioning

confidence: 99%

Controlling ligand substitution reactions of organometallic complexes: Tuning cancer cell cytotoxicity

Wang

Habtemariam

Geer

et al. 2005

Proc. Natl. Acad. Sci. U.S.A.

296

298

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Organometallic compounds offer broad scope for the design of therapeutic agents, but this avenue has yet to be widely explored. A key concept in the design of anticancer complexes is optimization of chemical reactivity to allow facile attack on the target site (e.g., DNA) yet avoid attack on other sites associated with unwanted side effects. Here, we consider how this result can be achieved for monofunctional ''piano-stool'' ruthenium(II) arene complexes of the type [( 6 -arene)Ru(ethylenediamine)(X)] n؉ . A potentially important activation mechanism for reactions with biomolecules is hydrolysis. Density functional calculations suggested that aquation (substitution of X by H2O) occurs by means of a concerted ligand interchange mechanism. We studied the kinetics and equilibria for hydrolysis of 21 complexes, containing, as X, halides and pseudohalides, pyridine (py) derivatives, and a thiolate, together with benzene (bz) or a substituted bz as arene, using UV-visible spectroscopy, HPLC, and electrospray MS. The x-ray structures of six complexes are reported. In general, complexes that hydrolyze either rapidly {e.g., X ‫؍‬ halide [arene ‫؍‬ hexamethylbenzene (hmb)]} or moderately slowly [e.g., X ‫؍‬ azide, dichloropyridine (arene ‫؍‬ hmb)] are active toward A2780 human ovarian cancer cells, whereas complexes that do not aquate (e.g., X ‫؍‬ py) are inactive. An intriguing exception is the X ‫؍‬ thiophenolate complex, which undergoes little hydrolysis and appears to be activated by a different mechanism. The ability to tune the chemical reactivity of this class of organometallic ruthenium arene compounds should be useful in optimizing their design as anticancer agents.anticancer ͉ bioorganometallic ͉ hydrolysis ͉ kinetics ͉ ruthenium complexes O rganometallic chemistry has evolved rapidly during the last 50 years, notably in areas related to catalysis and materials (1). Applications in biology and medicine are in their infancy, but the potential for exciting developments is clear (2). In the field of cancer chemotherapy, the cyclopentadienyl complex [Cp 2 TiCl 2 ] has been in clinical trials (3, 4), and a ferrocene derivative of Tamoxifen is a candidate for trials for breast cancer therapy (5). The successful design of second-and thirdgeneration platinum anticancer drugs, now widely used in the clinic, has demonstrated that detailed knowledge of the factors that control ligand substitution and redox reactions is very valuable in drug design. The chemical reactivity of the complexes can be chosen so as to balance the inertness required for the drug to reach its target site (e.g., DNA) and minimize attack on other sites (side effects) yet allow activation necessary for binding to the target. Thus, cis-[PtCl 2 (NH 3 ) 2 ], cisplatin, is relatively unreactive in high-chloride media (e.g., blood plasma) and is activated by hydrolysis near DNA in the nucleus (6). In contrast, carboplatin and oxaliplatin are relatively inert to hydrolysis, have a milder spectrum of side effects, and probably attack DNA by means of chelate ...

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“…These observations are in agreement with the stability of the ester bond observed for 3. [20], accessible from 2 in aqueous solution.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of a trinuclear cation [H3Ru3(Fc-arene)(C6Me6)2(O)]+ containing a ferrocenyl group tethered to an arene ligand

Vieille‐Petit

Unternährer

Therrien

et al. 2003

Inorganica Chimica Acta

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Triaqua(benzene)ruthenium(II) and triaqua(benzene)osmium(II): synthesis, molecular structure, and water-exchange kinetics

Cited by 117 publications

References 3 publications

Highly selective low-temperature hydrogenation of furfuryl alcohol to tetrahydrofurfuryl alcohol catalysed by hectorite-supported ruthenium nanoparticles

Highly selective low-temperature hydrogenation of furfuryl alcohol to tetrahydrofurfuryl alcohol catalysed by hectorite-supported ruthenium nanoparticles

Controlling ligand substitution reactions of organometallic complexes: Tuning cancer cell cytotoxicity

Synthesis of a trinuclear cation [H3Ru3(Fc-arene)(C6Me6)2(O)]+ containing a ferrocenyl group tethered to an arene ligand

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