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Condensation of 1,4-dichloropyridazine with pyrazole, 3,5-dimethylpyrazole and 3-methylpyrazole yielded two types of pyrazolyl-pyridazine ligands, viz., (i) products of substitution on one side of the pyridazine as 3-chloro-6-(pyrazolyl)pyridazine (Cl-L1), 3-chloro-6-(3,5-dimethylpyrazolyl)pyridazine (Cl-L2) and 3-chloro-6-(3-methylpyrazolyl)pyridazine (Cl-L3), and (ii) products of substitution on both sides such as 3,6-bis(pyrazolyl)pyridazine (L1), 3,6-bis(3,5-dimethylpyrazolyl)pyridazine (L2) and tautomers of 3,6-bis(3-methylpyrazolyl)pyridazine (L3). The reactions of eta6-areneruthenium complexes in methanol with the above mentioned pyrazolyl-pyridazine ligands form mononuclear complexes of the type [(eta6-arene)Ru(Cl-L)(Cl)]+ and [(eta6-arene)Ru(L)(Cl)]+; (arene = benzene and p-cymene; Cl-L = Cl-L1, Cl-L2, Cl-L3; L = L1, L2, L3). All these complexes are characterized by IR, NMR, mass spectrometry and UV-vis spectroscopy. The structures of some representative complexes are established by single crystal X-ray diffraction studies.

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

09/27/21 News Get Up To Speed Quickly On Emerging Topics: Dichloro(benzene)ruthenium(II) dimer

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The bond-assisted cyclometalation and phosphorus-carbon bond cleavage in (Arene)ruthenium(II) complexes are discussed. The complexes contain functionalized iminophosphorane-phosphine ligands Ph2PCH 2P{=NP(=X)(OR)2}Ph2 (X = O, S; R = Et, Ph). It is found that the functionalized iminophosphorane-phosphines act as versatile ligands upon coordination to a (eta6-arene)-ruthenium(II) fragment. The results show that the ligands are used as templates for the construction and stabilization of unusual organometallic ruthenium(II) complexes.

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Highly efficient and robust molecular ruthenium catalysts for water oxidation,
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The reaction of [{Ru(eta6-C6H6)Cl(mu-Cl)}2] with Py3COH in ethanol results in the formation of the cation [Ru(eta6-C6H6)(N,N?,O,-(C 5H4N)3CO)]+ which is isolated as its hexafluorphosphate salt 1. The cation acts as a ligand towards other transition metal ions. With Ag+ the hetero-trinuclear complex [{Ru(eta6-C6H6)((C5H 4N)3CO)}2Ag][PF6]3 2 is formed, while reaction with [Pd(PhCN)2Cl2] gives the bimetallic [Ru(eta6-C6H6)((C5H 4N)3CO)PdCl2][PF6] 3. Both compounds were fully characterised by spectroscopic methods and the trinuclear complex was additionally characterised by X-ray diffraction. Elsevier Science Ltd.

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

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A series of half-sandwich Ru(II) arene complexes of the type [Ru(eta6-arene)(L)Cl](PF6) 1-4, where arene is benzene (1, 2) or p-cymene (3, 4) and L is N-methylhomopiperazine (L1) or 1-(anthracen-10-ylmethyl)-4-methylhomopiperazine (L2), has been isolated and characterized by using spectral methods. The X-ray crystal structures of 2, 3 and 4 reveal that the compounds possess a pseudo-octahedral “piano- stool” structure equipped with the arene ligand as the seat and the bidentate ligand and the chloride ion as the legs of the stool. The DNA binding affinity determined using absorption spectral titrations with CT DNA and competitive DNA binding studies varies as 4 > 2 > 3 > 1, depending upon both the arene and diazacycloalkane ligands. Complexes 2 and 4 with higher DNA binding affinities show strong hypochromism (56%) and a large red-shift (2, 10; 4, 11 nm), which reveals that the anthracenyl moiety of the ligand is stacked into the DNA base pairs and that the arene ligand hydrophobicity also dictates the DNA binding affinity. In contrast, the monocationic complexes 1 and 3 are involved in electrostatic binding in the minor groove of DNA. The enhancement in viscosities of CT DNA upon binding to 2 and 4 are higher than those for 1 and 3 supporting the DNA binding modes of interaction inferred. All the complexes cleave DNA effectively even in the absence of an external agent and the cleavage ability is enhanced in the presence of an activator like H2O 2. Tryptophan quenching measurements suggest that the protein binding affinity of the complexes varies as 4 > 2 > 3 > 1, which is the same as that for DNA binding and that the fluorescence quenching of BSA occurs through a static mechanism. The positive DeltaH0 and DeltaS 0 values for BSA binding of complexes indicate that the interaction between the complexes and BSA is mainly hydrophobic in nature and the energy transfer efficiency has been analysed according to the Foerster non-radiative energy transfer theory. The variation in the ability of complexes to cleave BSA in the presence of H2O2, namely, 4 > 2 > 3 > 1, as revealed from SDS-PAGE is consistent with their strong hydrophobic interaction with the protein. The IC50 values of 1-4 (IC50: 1, 28.1; 2, 23.1; 3, 26.2; 4, 16.8 muM at 24 h; IC 50: 1, 19.0; 2, 15.9; 3, 18.1; 4, 9.7 muM at 48 h) obtained for MCF 7 breast cancer cells indicate that they have the potency to kill cancer cells in a time dependent manner, which is similar to cisplatin. The anticancer activity of complexes has been studied by employing various biochemical methods involving different staining agents, AO/EB and Hoechst 33258, which reveal that complexes 1-4 establish a specific mode of cell death in MCF 7 breast cancer cells. The comet assay has been employed to determine the extent of DNA fragmentation in cancer cells. The Royal Society of Chemistry 2014.

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Highly efficient and robust molecular ruthenium catalysts for water oxidation,
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Four new ruthenium arene PTA type complexes have been synthesized using substituted picolinamide derivatives as ancillary ligands and characterized by spectroscopic methods. In one of the complexes, the ancillary ligand has shown an unprecedented valence-bond tautomerization in the presence of an ammonium salt to act as a polar neutral donor ligand making the ligand more prone towards substitution. The same compound has shown remarkable antiproliferative activity against three cancer cell lines with GI50 values comparable to Adriamycin, a known therapeutic drug. Along with this it also strongly inhibits the action of thioredoxin reductase, which might be a probable reason for the enhanced proliferative action of the valence-bond tautomerized compound.

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Highly efficient and robust molecular ruthenium catalysts for water oxidation,
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The fragrances (S)-(+)- and (R)-(-)-canthoxal [(S)-(+)- and (R)-(-)-3-(4-methoxyphenyl)-2-methylpropanal] and (+)- and (-)-Silvial [(+)- and (-)-3-(4-isobutylphenyl)-2-methylpropanal] have been synthesized in high enantiopurity via a simple four-step strategy starting from the commercially available 4-substituted benzaldehydes. The key synthetic step is the catalytic asymmetric hydrogenation of the appropriate 3-aryl-2-methylacrylic acid which has been carried out employing an in situ prepared ruthenium/axially chiral phosphine catalyst (up to 98% ee). The olfactory activity of the single enantiomers has been evaluated.

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Highly efficient and robust molecular ruthenium catalysts for water oxidation,
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The late transition metal complexes [(Ar)RuCl2(PS)] (Ar = C6H6, o-MeC6H4(iPr) and C6Me6), [RuCl2(eta3:eta3- C10H16)(PS)], [RhCl(cod)(PS)] (cod = 1,5-cyclooctadiene) and [(Cp*)MCl2(PS)] (Cp* = pentamethylcyclopentadienyl, M = Rh or Ir) (where PS = Ph2PNHC6H4P(S)Ph2) have been synthesised by the reaction of Ph2PNHC6H4P(S)Ph2 with the appropriate chloride bridged transition metal dimers. In all of these complexes the ligand is monodentate P-bound. Chloride abstraction from representative complexes, using Ag[ClO4], gave the cationic compounds [(o-MeC6H4{iPr})RuCl(PS)][ClO4], [Rh(cod)(PS)][ClO4] and [(Cp*)RhCl(PS)][ClO4] in which the ligand is k2-P,S bound. All new compounds were characterised by a combination of 31P{1H} and 1H NMR spectroscopy, microanalysis, FAB mass spectrometry and IR spectroscopy. The molecular structures of five complexes have been determined by single-crystal X-ray diffraction – both monodentate and chelate coordination has been characterised. The P-monodentate compounds all display intramolecular N-H?S hydrogen bonding.

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Highly efficient and robust molecular ruthenium catalysts for water oxidation,
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The invention relates to a process for the reduction of compounds comprising a carbon-carbon (C=C), carbon-oxygen (C=O), or carbon-nitrogen (C=N) double bond, to a corresponding hydrogenated alkane, alcohol or amine, comprising contacting a compound comprising the C=C, C=O or C=N double bond with a hydrogen donor solvent and a catalyst comprising a metal complex having a tridentate aminodiphosphine ligand under transfer hydrogenation conditions.

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

Sep-21 News Awesome Chemistry Experiments For Dichloro(benzene)ruthenium(II) dimer

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The cyclometalation of chiral secondary amines through ortho-metalation of an aryl group occurred readily with [(eta6-benzene)RuCl 2]2 in acetonitrile. Reasonable to good yields of the expected cationic products of the form [(eta6-benzene)Ru(N-C)(NCMe) ](PF6), in which N-C represents the cyclometalated ligands, were obtained with bis-(R)-phenylethylamine, bis-(R)-1-naphthylethylamine, and (2R,5R)-2,5-diphenylpyrrolidine. Variable proportions of the expected four diastereoisomers were found according to NMR studies. The stereochemistry of complexes was investigated by 2D NMR in solution and by X-ray diffraction of single crystals. The (S) configuration at the metal was generally associated with a delta conformation of the metallacycle, and conversely, the (R) configuration with the lambda conformation.

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

9/22 News Awesome Chemistry Experiments For Dichloro(benzene)ruthenium(II) dimer

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Schiff base (L) synthesized by reacting 2-methylthiobenzeldehyde with 2-(phenylseleno)ethylamine on reaction with di-mu-chlorobis{eta6-benzene)dichloro-ruthenium(II)}(a) forms two type of species: (i) [Ru(L)2][PF6]2 (1) [L:a = 4:1 and reaction time ?8 h] and (ii) [Ru(eta6-C6H6)(L)][PF6]2 (2) [L:a = 2:1 and reaction time ?1 h]. This is first example in which chloro as well benzene ring both are successively substituted by controlling metal:ligand ratio and duration of reaction. The geometry around Ru in complex 1 is distorted octahedral. The 2 has a pseudo-octahedral half sandwich “piano-stool” disposition of ligands around Ru. The Ru-Se distances are 2.4683(10)-2.5082(7) A??. The proton and carbon-13 NMR spectra of L and its both complexes 1 and 2 authenticate them. The 2 shows high catalytic activity for oxidation of primary and secondary alcohols both (TON upto 9.6 × 104; TOF upto 4.80 × 104 h-1).

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