Discovery of Dichloro(benzene)ruthenium(II) dimer

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A novel approach to design bimetallic anticancer drug candidates with the capability to combat both drug resistance and tumor metastasis is reported. These water-soluble bifunctional Pt(iv)-Ru(ii) heterodinuclear complexes with a unique mode of action display up to 2-orders of magnitude enhanced cytotoxicity in cisplatin-resistant cells and significantly impede cancer cell migration.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

Brief introduction of Dichloro(benzene)ruthenium(II) dimer

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The invention relates to a method for producing statins known as HMG-CoA reductase inhibitors. Some of the intermediate compounds used in the inventive method are novel compounds. The invention also relates to said novel intermediate compounds.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

Some scientific research about Dichloro(benzene)ruthenium(II) dimer

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The complex [(eta5-MeC5H4)Ru(DPVP)2(CH3 CN)]PF6 (4) (DPVP = Ph2PCH=CH2) loses CH3CN under vacuum to produce the phosphaallyl complex [(eta5-MeC5H4)Ru(eta1-DPVP)( eta3-DPVP)]PF6 (6) and reacts with Me3SiC?CH and PhC?CH in CH2Cl2-CH3OH solutions to form the methoxymethylcarbene [(eta5-MeC5H4)(DPVP)2Ru=C(OCH 3)(CH3)]PF6 (7) and the carbonyl complex [(eta5-MeC5H4)Ru(DPVP)2(CO)]PF 6 (8), respectively. In contrast [(eta5-MeC5H4)Ru(DPVP)(CO)(CH3CN)] PF6 (15) does not lose CH3CN to form a phosphaallyl complex. The structures of the complexes described herein have been deduced from elemental analyses, infrared spectroscopy, 1H, 13C{1H}, 1H NOE, where appropriate by 31P{1H} NMR spectroscopy and in eight cases by X-ray crystallography.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

New explortion of Dichloro(benzene)ruthenium(II) dimer

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Novel multidentate pyridyl-aminophosphinite (L1) and pyridyl-phosphoramidite (L2) ligands of N^P^P^N-donor system have been synthesized via a series of simple steps. The ligands are symmetrical and as a result, their reactions with [Ru(p-cymene)Cl2]2 and [Ru(benzene)Cl2]2 lead to the formation of four monodentate bimetallic complexes (1?4) that retain the symmetry of the ligands. Meso and racemic mixtures (rac) of bidentate bimetallic complexes 5?8 were formed from the monodentate complexes through coordination of the pyridine nitrogen atoms to the two metal centers. The isomerism occurs at each metal center, which was evidenced by 31P{1H}, 1H NMR spectroscopy and single-crystal X-ray diffraction. The complexes were active towards hydrogenation of levulinic acid (LA) to gamma-valerolactone (GVL) using formic acid as the hydrogen source. The complexes are active at relatively low temperatures and are able to perform the hydrogenation in the absence of any additional solvent apart from the reagents to give high TON of 3 600. The catalysts are recyclable up to the fourth cycle, following which 20 % loss of activity is seen.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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On the basis of isolated diastereomeric triorganylstannyl-P 5-deltacyclenes 7? and 7?, almost pure enantiomers of their destannylation products 8? and 8? are now available. These stereochemically inert cage chiral species contain a configurationally labile P1-H1 group that defines two epimers 8a and 8b of each of the enantiomers, which are connected by a rapid equilibrium. Mirror-symmetric circular dichroism (CD) spectra of the enantiomeric cages are compatible with the identification of epimers. A simulation of the CD spectrum of the major epimer 8?a relates the cage chirality of the system to the observed chiroptical effects. Both cage epimers and two of the phosphorus cage atoms are active as ligands with respect to [M(CO)5] fragments of Cr, Mo, and W. Four almost isoenergetic regio- and stereoisomers of the resulting mononuclear complexes are formed for these metals, but only one of the isomers per metal crystallized in the case of the racemic series of the complexes. The enantiopure versions of cages and cage complexes, however, did not crystallize at all, a well-known phenomenon for chiral compounds. CD spectra of the optically active complex isomer mixtures are close to identical with the CD spectra of the related free cages and point again to the chiral cages as the dominant source of the CD effects of the complexes. [(Benzene)RuCl2] complexes of the cage ligand 8 behave totally differently. Only a single species 12=[(benzene)RuCl2 8b] is formed in almost quantitative yield and the minor epimer 8b plays the role of the ligand exclusively. The reaction works as well for the separated enantiomeric cage versions to yield the highly enriched enantiomers 12? and 12? separately. An efficient kinetic resolution process was identified as the main reason for this finding. It is based on a high stereo- and regiochemical flexibility of the P-C cage ligand that is capable of adjusting to the specific requirements of a suitable transition-metal complex fragment. Such ligand flexibility is regularly observed in metalloenzymes, but is a very rare case in classical and organometallic complex chemistry. A rigid cage structure combined with a configurationally labile P-H center generates cage epimers of P5-deltacyclenes. In spite of five competing Patoms and the epimeric nature of the ligand, the [(benzene)RuCl2] unit forms a single complex only by kinetic resolution of the minor ligand epimer (see figure). P5-Deltacyclenes are thus bulky chiral ligands capable of adjusting their stereochemical properties according to the specific requirements of a transition-metal complex fragment.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

Top Picks: new discover of Dichloro(benzene)ruthenium(II) dimer

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The complex (dippe = 1,2-bis(diisopropylamino)ethane reacts with cyclohexadienyl-lithium in tetrahydrofuran yielding a dark mixture, from which the hydrido-arene complex (1) can be isolated in moderate yields upon treatment with MeOH-NaBPh4. 1, as well as the toluene complex (2), can be prepared by reaction of with n-BuLi in benzene or toluene respectively, followed by MeOH-NaBPH4.The ruthenium complexes 2> with dippe and Ag+, and isolated as the tetraphenylborate salts 3.These compounds react with NaBH4 in acetone-ethanol furnishing the hydrido-arene derivatives (L = C6H6 5, p-cymene 6).All the compounds were characterized by IR, NMR and microanalysis.The X-ray crystal structures of 3 and 4 are also reported.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

A new application about Dichloro(benzene)ruthenium(II) dimer

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The synthesis and characterization of heteroleptic complexes with the formulations [(eta6-arene)RuCl(fcdpm)] (eta6-arene = C6H6, C10H14) and [(eta5-C5Me5)MCl(fcdpm)] (M = Rh, Ir; fcdpm = 5-ferrocenyldipyrromethene) have been reported. All the complexes have been characterized by elemental analyses, IR, 1H NMR and electronic spectral studies. Structures of [(eta6-C6H 6)RuCl(fcdpm)] and [(eta6-C10H 14)RuCl(fcdpm)] have been determined crystallographically. Chelating monoanionic linkage of fcdpm to the respective metal centres has been supported by spectral and structural studies. Further, reactivity of the representative complex [(eta6-C10H14)RuCl(fcdpm)] with ammonium thiocyanate (NH4SCN) and triphenylphosphine (PPh 3) have been examined.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Ruthenium (Ru)-based complexes show promising prospect for development of anticancer agents. Among the cytotoxic Ru complexes, Ru arene complexes are famous for their comparatively high solubility in water under physiological conditions. However, more information is needed to understand the roles and effects of aquation reaction on the anticancer efficacy of these metal complexes. Herein, the aquation process of a Ru(II) arene complex [Ru(II) (C6H6) (3-MOIP)Cl]Cl (RuMOP) with potent anticancer activity was examined and characterized by UV?vis spectrometry, mass spectrometry, 1H NMR spectrometry and HPLC analysis. The results reveal that, aquation reaction occurred quickly in aqueous solution, with the chloride ligand replaced by hydrone. Moreover, the aquation process changed the complex’s cellular uptake in tumour cells, finally affected its antiproliferative activity. The parent complex RuMOP could activate the caspase family proteins and p53 signaling pathways, showed high-level interaction with tumour cell membrane and death receptors. However, these cellular events and signaling could be blocked by aquation reaction. Taken together, these results help us to understand the anticancer action mechanisms of arene Ru complexes and provide important information for rational design of such kind of metal complexes with better cancer therapeutic potency.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

Brief introduction of Dichloro(benzene)ruthenium(II) dimer

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The invention relates to an enantiomerically enriched chiral compound comprising a transition metal M, which comprises four, five or six coordinating groups of which at least one pair is linked together to form a bidentate ligand, in which M is directly bound via one single ?-bond to a carbon atom of an optionally substituted and/or optionally fused (hetero)aromatic ring of said bidentate ligand and in which M is directly bound to a nitrogen atom of a primary or secondary amino group of said bidentate ligand, thereby forming a metallacycle between said bidentate ligand and the metal M, said metal M being selected from the metals of groups 8 and 9 of the Periodic Table of the Elements, in particular iron, ruthenium, osmium, cobalt, rhodium, or iridium. The chiral compound can be used as a catalyst, preferably in an asymmetric transfer hydrogenation process. The invention further relates to a process for an asymmetric transfer hydrogenation of a prochiral compound in the presence of a hydrogen donor and the chiral compound of the invention comprising a transition metal chosen from the metals of groups 8, 9 and 10 of the Periodic Table, in particular iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium or platinum as the catalyst.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

Awesome Chemistry Experiments For Dichloro(benzene)ruthenium(II) dimer

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The cyclometalation of chiral and achiral primary amines occurred readily with Ru(II), Rh(III), and Ir(III) derivatives. Thus, the metalation of (R)-1-phenylethylamine by [(eta6-benzene)RuCl2] 2, [(eta5-Cp*)-RhCl2]2 and [(eta5-Cp*)IrCl2]2 was studied. Good yields of the expected cationic products in which the phenyl group was ortho-metalated were obtained for the rhodium and the ruthenium derivatives, whereas a mixture of products was formed in the case of the iridium complex. Benzylamine, (R)-1-phenylpropylamine, (R)-1-(1-naphthyl)ethylamine, and (R)-1-aminotetraline afforded also the cycloruthenation products whose general formula is [(eta6-benzene)Ru(N-C)(NCMe)]PF6 where N-C represents the orthometalated ligands. Substitution of the acetonitrile ligand by PMe2Ph occurred readily on the ruthenium complexes, affording stable compounds that were characterized by X-ray diffraction studies on single crystals, thus ascertaining the existence of the cycloruthenated five-membered rings. Accurate analyses of the structure of the complexes were implemented in solution and in the solid state. The (S) configuration at the metal was usually associated with a delta conformation of the metallacycle, and conversely, the (R) configuration with the lambda conformation. The study of the conformation of the five-membered rings revealed that the orientation of the NH2 group is such that one NH unit is oriented toward the eta6-benzene ring (roughly parallel to the Ru-centroid benzene vector), whereas the second NH is parallel to the Ru-L bond, L = NCMe or PMe2Ph.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI