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Transition metal chemistry of phosphorus based ligands. Ruthenium(II) chemistry of bis(phosphino)amines, X2PN(R)PX2 (R=H or Ph, X=Ph; R=Ph, X2=O2C6H4)

Reactions of CpRuCl(PPh3)2 with bis(phosphino)amines, X2PN(R)PX2 (1 R=H, X=Ph; 2 R=X=Ph; 3 R=Ph, X2=O2C6H4) give neutral or cationic mononuclear complexes depending on the reaction conditions. Reaction of 1 with CpRuCl(PPh3)2 gives one neutral complex, [CpRu(Cl)(eta2-Ph2PN(H)PPh2)] (4) and two cationic complexes, [CpRu(eta2-Ph2PN(H)PPh2)(eta1-Ph 2PN(H)PPh2)]Cl (5) and [CpRu(PPh3)(eta2-Ph2PN(H)PPh2)]Cl (6), whereas the reaction of 2 with CpRuCl(PPh3)2 leads only to the isolation of cationic complex, [CpRu(PPh3)(eta2-Ph2PN(Ph)PPh2)]Cl (7). The catechol derivative 3, in a similar reaction, affords an interesting mononuclear complex [CpRu(PPh3){eta1-(C6H4O2)PN(Ph)P(O2H4C6)}2]Cl (8) containing two monodentate bis(phosphino)amine ligands. The structural elucidation of the complexes was carried out by elemental analyses, IR and NMR spectroscopic data.

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

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Synthesis, catalytic properties and biological activity of new water soluble ruthenium cyclopentadienyl PTA complexes [(C5R5)RuCl(PTA)2] (R = H, Me; PTA = 1,3,5-triaza-7-phosphaadamantane).

The new water soluble ruthenium complexes [(C5R5)RuCl(PTA)2] (R = H, Me; PTA = 1,3,5-triaza-7-phosphaadamantane) were synthesised and characterised. Their evaluation as regioselective catalysts for hydrogenation of unsaturated ketones in aqueous biphasic conditions and as cytotoxic agents towards the TS/A adenocarcinoma cell line is briefly presented.

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

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The synthesis of an anionic, tetraphenylborate-functionalized, [P,N]-hybrid phosphinobenzimidazole ligand and its hemilabile behaviour in ruthenium zwitterion chemistry

A new anionic [P,N]-hybrid ligand based on a phosphinobenzimidazole scaffold and functionalized with a tetraphenylborate substituent is reported. This new anionic ligand readily chelates to a variety of ruthenium- cyclopentadienyl and -pentamethylcyclopentadienyl precursors to form a series of zwitterionic ruthenium piano-stool complexes (eta5-C 5R5)Ru(L)(kappa2-P,N) (R = H or Me; L = CO or PPh3). In the presence of excess CO or 1-alkynes, the chelate complexes undergo ring-opening of the kappa2-P,N ligand at the ruthenium-nitrogen bond (in some cases reversibly) under relatively mild conditions. In particular, the reactions with 1-alkynes proceed via vinylidene intermediates which subsequently insert into the ruthenium-nitrogen bond of the kappa2-P,N ligand.

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

A catalyst don’t appear in the overall stoichiometry of the reaction it catalyzes, but it must appear in at least one of the elementary reactions in the mechanism for the catalyzed reaction. 92361-49-4, Name is Chloro(pentamethylcyclopentadienyl)bis(triphenylphosphine)ruthenium(II), molecular formula is C46H45ClP2Ru. In a Article£¬once mentioned of 92361-49-4, Quality Control of: Chloro(pentamethylcyclopentadienyl)bis(triphenylphosphine)ruthenium(II)

Transition metal alkynyl complexes by transmetallation from Au(CXiCAr)(PPh3) (Ar = C6H5 or C 6H4Me-4)

Facile acetylide transfer reactions take place between gold(i) complexes Au(CXiCAr)(PPh3) (Ar = C6H5 or C 6H4Me-4) and a variety of representative inorganic and organometallic complexes MXLn (M = metal, X = halide, Ln = supporting ligands) featuring metals from groups 8-11, to afford the corresponding metal-alkynyl complexes M(CXiCR)Ln in modest to good yield. Reaction products have been characterised by spectroscopic methods, and molecular structure determinations are reported for Fe(CXiCC6H 4Me-4)(dppe)Cp, Ru(CXiCC6H4Me-4)(dppe) Cp*, Ru(CXiCC6F5)(eta2-O 2)(PPh3)Cp*, Ir(CXiCC6H 4Me-4)(eta2-O2)(CO)(PPh3) 2, Ni(CXiCC6H4Me-4)(PPh3)Cp and trans-Pt(CXiCAr)2L2 (Ar = C6H5, L = PPh3; Ar = C6H4Me-4, L = PPh3, PMe3). The Royal Society of Chemistry 2009.

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

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Optically active transition metal complexes. XCVIII. Synthesis and structure of diastereomers of <(-)-Norphos>Ru(II)(eta5-C5H5)I

Two diastereomers of the <(-)-Norphos>Ru(II) complex with eta5-C5H5 and iodide as ligands were synthesized by a phosphine-exchange reaction between (Ph3P)2Ru(II)(eta5-C5H5)Cl and (2R,3R)-(-)-Norphos, followed by Cl/I displacement.Each of the diastereomers can be separated and their structures and chiroptical properties are discussed on the basis of 1H NMR spectroscopy, circular dichroism, and X-ray crystallography.

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

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Reactions of ruthenium Cp phosphine complex with 4,4-disubstituted-1,6- enynes: Effect of methyl substituents in the olefinic fraction

We studied chemical reactions of Cp(PPh3)2RuCl with nine 1,6-enyne compounds (1-4, 8, 12, 19, 21, and 22) in which the triple bond is associated with propargylic alcohol and the olefinic group has various substituted methyl groups. For the enyne compounds 1-3 with no substituted methyl group, the reaction takes place at the propargylic alcohol first giving the allenylidene complex 6 which could undergo a skeletal rearrangement to yield the disubstituted vinylidene complex 7. By changing the propargylic alcohol to propargylic ether, the reaction gives the carbene complex 10 as the major product and the butadiene complex 9 by a cyclization reaction as the minor product. For enyne 12 with two methyl groups at the terminal carbon of the olefinic part, formation of either of the carbene complexes 15 and 16 with a substituted cyclopentenyl ring at Calpha or the vinylidene complex 17 is controlled by the use of solvent. For the formation of 15 and 16, a C-C bond-forming cyclization reaction is proposed to occur at Cbeta in an intermediate where the triple bond is pi-coordinated. However, for the vinylidene intermediate, the reaction may proceed by the formation of the allenylidene, which undergoes a retro-ene reaction to bring about cleavage of the dimethyl substituted allyl group giving 17. For two enynes 21 and 22 where each olefinic portion is internally substituted with one methyl group, two vinylidene complexes 23 and 24 each with a five-membered ring bonded at Cbeta are isolated. The reaction proceeds via formation of an allenylidene intermediate followed by a cyclization at Cgamma. Stabilization of the cationic charge by the presence of methyl subsituents clearly controls the reaction pathway to give different products. These chemical reactions and their mechanisms are corroborated by structure determinations of five ruthenium complexes using single crystal X-ray diffraction analysis.

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

The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.32993-05-8, Name is Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II), molecular formula is C41H35ClP2Ru. In a Article£¬once mentioned of 32993-05-8, Recommanded Product: 32993-05-8

Caenorhabditis elegans as a model for exploring the efficacy of synthesized organoruthenium complexes for aging and Alzheimer’s disease a neurodegenerative disorder: A systematic approach

The current article deals with the preparation and characterisation of new organoruthenium(II) complexes, namely [RuCp(Dea-Sal-tsc)(PPh3)] (1), [RuCp(Dea-Sal-mtsc)(PPh3)] (2), [RuCp(Dea-Sal-etsc)(PPh3)] (3) and [RuCp(Dea-Sal-ptsc)(PPh3)] (4). The new ruthenium(II) complexes were characterized by various analytical, spectral techniques. The structure of the ligand [H2-Dea-Sal-tsc] and the complex [RuCp(Dea-Sal-tsc)(PPh3)] (1) were confirmed by X-ray crystallography. The complexes (1?4) were used to study the toxicity, stress resistance, aging and neuro-protective effects by taking Caenorhabditis elegans as model. In?vitro free radical scavenging activity was performed by DPPH free radical scavenging assay, the complexes (1?4) exhibited highest scavenging activity than standard Vitamin C (IC50?=?5.28?¡À?0.10). The lifespan has increased over 22.4% in mev-1 mutant worms treated with complex 4. The complex 4 triggered the DAF-16 nuclear localization, increases sod-3 expression and reduced amyloid (Abeta) protein induced paralysis were observed. In the present study we confirmed that oxidative stress resistance of N2 and lifespan extension of mev-1 mutant which showed the potential ROS scavenging activity of complex 4. The results also confirmed the effective anti-aging potential of ruthenium complex 4 which may be developed as a therapeutic drug for the prevention of aging and age related neurodegenerative diseases. Further studies are required to find out the exact action of complex 4 on higher model.

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

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Synthesis and characterization of some cationic ruthenium(II) complexes based on polypyridyl ligand

The cationic mononuclear complexes [Ru(eta5-arene) (kappa2-dpp)(EPh3)]+ (eta5-arene = C5H5 (1), C5Me5 (2), C 9H7 (3); E=P (1a, 2, 3), As (1b); dpp = 2,3-bis(2-pyridyl) pyrazine) resulting from the reactions of [Ru(eta5-arene)(EPh 3)2Cl] with dpp in equimolar ratio in methanol under refluxing conditions, containing both group 15 donor and a planar polypyridyl ligand are reported here. These complexes have been isolated as their hexafluorophosphate salts and fully characterized by elemental analyses and spectral techniques, viz. IR, 1H and 31P NMR, FAB-MS and electronic spectral studies.

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

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Reactions of (L = PPh3, AsPh3, or SbPh3; L2 = Ph2PCH2CH2PPh2 or Ph2PCH2PPh2) with 1,4-Piperazinedicarbonitrile or 1-Piperidinecarbonitrile in the Presence of an Anion (BF4(1-), PF6(1-), BPh4(1-), or ClO4(1-))

Reactions of (L = PPh3, AsPh3, or SbPh3; L2 = Ph2PCH2CH2PPh2 or Ph2PCH2PPh2) have been carried out with 1-piperidinecarbonitrile or 1,4-piperazinedicarbonitrile in the presence of a suitable anion (PF6(1-), BF4(1-), BPh4(1-), or ClO4(1-)).The products were found to be cationic mono- and bi-nuclear complexes which have been characterised by elemental analyses and spectroscopic (i.r., u.v.-visible, and n.m.r.) studies.Conductivity measurements have also been carried out to confirm the charges on these cationic species.

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

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Dimeric ruthenium complexes with C5H2 and C5H bridges

Treatment of [Cp*Ru(dppe)]BF4 with 0.5 equiv of HC?CCH(OH)C?CH in THF led to the formation of the C5H2-bridged compound [Cp*(dppe)-Ru=C=C=CHCH=C=Ru(dppe)Cp*](BF4)2. The C5H2-bridged compound reacted with alumina to give the C5H2-bridged compound [Cp*(dppe)Ru=C=C=CHC?CRu-(dppe)Cp.*]BF4. These reactions were extended to prepare the analogous complex [Cp(PPh3)2Ru=C=C= CHC?CRu(PPh3)2Cp]BF4.

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