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Bis(allyl) Ruthenium(IV) Complexes. Part 2. Ruthenium Complexes containing ?- and mu-Pyrazine and ?- and mu-Bis(diphenylphosphino)methane (dppm) Ligands. Crystal Structures of <2(mu-dppm)>*Me2CO*CH2Cl2 and …

Reaction of <2> 1 (C10H16 = 2,7-dimethyloctadienediyl) with one equivalent of pyrazine (pyz) or bis(diphenylphosphino)methane (dppm) leads to the formation of the neutral dimeric products <2(mu-pyz)> 2a and <2(mu-dppm)> 2b respectively.The neutral monomeric complexes 3a ad 3b are obtained by reacting 1 with two equivalents of pyz and dppm respectively.The mixed valence diruthenium complex <(mu-dppm)> 5 is readily obtained from the reaction of 3b with <2> 4.The X-ray structures of complex 2b (no.2), a = 11.914(1), b = 11.943(2), c = 19.524(2) Angstroem, alpha = 105.79(1), beta = 107.64(1), gamma = 91.01(1) deg, Z =2>, and complex 5 are reported.

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

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Organometallic ionic liquids from half-sandwich Ru(II) complexes with various chelating ligands

Salts comprising of cationic half-sandwich Ru(II) complexes with various chelating ligands and the bis(trifluoromethanesulfonyl)amide anion (Tf2N-) were prepared. These salts can be represented as [(arene)RuCl(L-L)][Tf2N] (arene = C6Me5Bu, C6Me6, p-cymene, C6H6; L-L = 2-Py-CH2NHCMe2Et, 2-Py-CH=NC6H13, H13C6NHCH2CH2NHC6H13, Me2NCH2CH2SC4H9, Me2CN=CHCH=NCMe2). Two of the eight salts are liquids at room temperature (?20 C), while the other salts are solids with melting points of 60-130 C. Upon cooling from the melt, most salts exhibited glass transitions between -30 C and -5 C. The salts were found to catalyze the oxidation of cyclohexanol although decomposition occurred during the reaction. Crystal structures of related salts were also determined.

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

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Benzimidazoles as ligands in the ruthenium-catalyzed enantioselective bifunctional hydrogenation of ketones

A series of Cl2Ru(diphosphane)L2 (II) complexes in which L = N1-alkylated benzimidazoles, bonding to the metal through nitrogen, have been synthesized and characterized. In the case of 1-methylbenzimidazole, the resulting complexes exist as statistical mixtures of all possible conformational isomers. When the size of the substituent on the benzimidazole was increased to complexes could be prepared that exist as a single diastereomer. All complexes possessing benzimidazole ligands bound to the ruthenium center are active for the mild and chemoselective hydrogenation of ketones in the presence of alkenes. Catalysts that exist as a single diastereomer, prepared with enantiomerically pure diphosphanes, catalyze the hydrogenation of prochiral ketones with moderate levels of enantioselectivity that are significantly improved relative to catalysts existing in several conformations.

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

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Organometallic ruthenium(II) scorpionate as topo IIalpha inhibitor; In vitro binding studies with DNA, HPLC analysis and its anticancer activity

New organoruthenium [(eta6-arene)RuII(L)Cl]Cl (1: arene = p-cymene, L = L1; 2: arene = p-cymene, L = L2; 3: arene = benzene, L = L1; 4: arene = benzene; L = L2; L1 = bis(3,5-dimethylpyrazolyl)parabenzoic acid, L2 = bis(3,5-dimethylpyrazolyl)metabenzoic acid) have been synthesized and characterized by analytical and spectroscopic methods. The molecular structure of [(eta6-p-cymene)RuCl(L1)]Cl (1) was determined by single crystal X-ray diffraction studies. Preliminary in vitro binding studies of 1-4 with CT DNA were carried out by employing various biophysical techniques which revealed their avid DNA binding via non-covalent binding mode viz; partial intercalation of the eta6-arene group as well as electrostatic surface interaction through one oxygen atom of the phosphate backbone of the DNA helix; however, complexes 1 and 3 display higher binding propensity in comparison to 2 and 4, as quantified by Kb. The interaction was further analysed by HPLC technique. The results of the cleavage experiments of pBR322 DNA with 1 and 3 displayed significantly good cleavage at 20-40 muM, following the oxidative pathway. These findings have revealed that the hydrophobic arene, and the chloride leaving group have important roles in the novel mechanism of recognition of DNA by (eta6-arene)ruthenium(II) complexes, and will aid the design of more effective anticancer complexes, as well as new site-specific DNA reagents. Furthermore, the anticancer activity of the complexes 1 and 3 on 15 cell lines of different histological origin has been studied. It has been observed that 1 exhibits higher cytotoxicity than 3, and the cells undergo apoptotic cell death.

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

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Preparation of chiral imidazolin-2-imine ligands and their application in ruthenium-catalyzed transfer hydrogenation

2-Chloro-1,3-diisopropyl-4,5-dimethylimidazolium tetrafluoroborate (1) serves as a convenient starting material for the preparation of mono- and bis(imidazolin-2-imine) ligands. Thus, the reaction of two equivalents of 1 with 1,2-ethylenediamine in the presence of potassium fluoride afforded the bis(2-aminoimidazolium) salt [BLiPrH2][BF4]2 (2), from which the achiral bis(imidazolin-2-imine) ligand N,N?-bis(1,3-diisopropyl-4,5-dimethylimidazolin-2-ylidene)-1,2-ethanediamine (BLiPr) can be obtained by deprotonation. Likewise, the reaction of 1 with (1R,2R)-(-)-1,2-diaminocyclohexane (DACH) gave [DACH(ImiPrH)2][BF4]2 (3) and its deprotonation the chiral, C2-symmetric diimine DACH(ImiPr)2 (4). Under similar conditions, chiral, C1-symmetric mono(imidazolin-2-imines) were obtained from the reaction of 1 with one equivalent of (1R,2R)-(-)-1,2-diaminocyclohexane (DACH) or (1S,2S)-(-)-1,2-diphenylethylenediamine (DPEN), which afforded the 2-aminoimidazolium salts [DACH(ImiPrH)NH2][BF4] (5) and [DPEN(ImiPrH)NH2][BF4] (6), respectively. The reaction of 4 with [(C6H6)RuCl2]2 gave ruthenium complex [(C6H6)Ru{DACH(ImiPr)2}]Cl2, [7]Cl2, which was treated with KPF6 to form [7][PF6]2. The ligand precursors 5 and 6 were deprotonated in the presence of [(C6H6)RuCl2]2, which resulted in the formation of complexes [(C6H6)Ru{DACH(ImiPr)NH2}Cl]Cl [8]Cl and [(C6H6)Ru{DPEN(ImiPr)NH2}Cl]Cl [9]Cl. Complexes [7][PF6]2, [8]Cl and [9]Cl were investigated for their ability to catalyze the transfer hydrogenation of acetophenone in isopropanol. Complex [8]Cl proved to be the most active system, while complex [9]Cl produced the highest enantioselectivity, albeit of only 27% ee. The molecular structures of [7][(C6H6)RuCl3]2¡¤CH2Cl2, formed as a side product, and of [8]Cl¡¤acetone were determined by X-ray diffraction analyses.

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

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Preparation and study of functionalized 1,2,4-triazine derivatives of the (eta6-arene)Ru(II) (arene=benzene or p-cymene) and (eta5-C5Me5)Rh(III) moieties

In dichloromethane the complexes [{(eta6-arene)RuCl(mu-Cl)}2] (arene=benzene or p-cymene) and [{(eta5-C5Me5)RhCl(mu-Cl)}2] react with the triazines 4-amino-6-methyl-5-oxo-3-thioxo-2,3,4,5-tetrahydro-1,2,4-triazine (3-S-ATAZ), 4-amino-6-methyl-5-oxo-3-phenylamino-4,5-dihydro-1,2,4-triazine (3-PhNH-ATAZ) and 4-amino-6-methyl-5-oxo-3-amino-4,5-dihydro-1,2,4-triazine (3-NH2-ATAZ) to form the corresponding complexes [(eta6-arene)RuCl(triazine)]Cl. The new compounds have been characterized by conductance measurements and spectroscopic (IR, (1)H, (13)C) methods. In every case the triazine acts as a chelating bidentate ligand, which has been confirmed by a single-crystal diffraction study carried out with [(eta5-C5Me5)RhCl(3-PhNH-ATAZ)]PF6*H2O.

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

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Optimizing the photovoltaic performance of thiocyanate-free ruthenium photosensitizers by structural modification of C^N cyclometalating ligand in dye-sensitized solar cells

Five new thiocyanate-free ruthenium(II) complexes with different electron-donating functionalized cyclometalating ligands C^N were synthesized, characterized and applied as photosensitizers in dye-sensitized solar cells (DSSCs). Their photophysical, electrochemical, thermal and photovoltaic properties have been investigated and density functional theory (DFT) calculations have been carried out on these dyes. These dyes exhibit good thermal stability with the onset decomposition temperature at 5% weight-loss (Td) of around 330 C. The DSSC device using the Ru(II) dye with the 9-tolylcarbazole chromophore exhibited the highest power conversion efficiency (eta) up to 3.39%, with a short-circuit photocurrent density (Jsc) of 8.06 mA cm-2, an open-circuit photovoltage (Voc) of 0.62 V and a high fill factor (ff) of 0.68 under illumination of an AM 1.5 solar cell simulator.

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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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A convenient one-pot synthesis of a functionalized-arene ruthenium half-sandwich compound [RuCl2(eta6-C6H 5OCH2CH2OH)]2

Reaction of RuCl3¡¤xH2O with 1-methoxy-1,4-cyclohexadiene in an alcohol solvent, ROH, gives [RuCl 2-(eta6-C6H5OR)]2 (R = Me, Et, or HOCH2CH2) in up to 79% yield. The crystal structures of [Ru2(mu-Cl3)(eta6-C 6H5-OEt)2]+[BPh4] – and [RuCl2(eta6-C6H 5OCH2CH2OH)]2 are also reported.

Sometimes chemists are able to propose two or more mechanisms that are consistent with the available data.Safety of Dichloro(benzene)ruthenium(II) dimer, If a proposed mechanism predicts the wrong experimental rate law, however, the mechanism must be incorrect.Welcome to check out more blogs about 37366-09-9, in my other articles.

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

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Novel microwave synthesis of half-sandwich [(eta6-C 6H6)Ru] complexes and an evaluation of the biological activity and biochemical reactivity

We have used a novel microwave-assisted method to synthesize a pair of half-sandwich ruthenium-arene-thiosemicarbazone complexes of the type [(eta6-C6H6Ru(TSC)Cl]PF6. The thiosemicarbazone (TSC) ligands are 2-(anthracen-9-ylmethylene) hydrazinecarbothioamide and 2-(anthracen-9-ylmethylene)-N- ethylhydrazinecarbothioamide derived from 9-anthraldehyde. The complexes are moderately strong binders of DNA, with binding constants of 104 m-1. They are also strong binders of human serum albumin, having binding constants of the order of 105 m-1. The complexes show some in vitro anticancer activity against human colon cancer cells, Caco-2 and HCT-116, with positive therapeutic indices. They did not show any activity as antibacterial agents against the organisms that were studied. Copyright

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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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Optically active P5-deltacyclenes: Selective oxidation, ligand properties, and a diastereoselective rearrangement reaction

Cage-chiral tetra-tert-butyl-P5-deltacyclene 5 is accessible as a pair of highly enriched enantiomers 5? and 5?. The only secondary phosphorus atom P1 of the cage can be selectively oxidized by reaction with t-BuOOH. The P1-oxo species 9a? and 9a?, allow the direct determination of their ee values. Oxidation occurs with the complete retention of the optical activity of the compounds. The chiroptical properties of 9a? and 9a? are strongly dominated by their cage chirality, the oxygen atom does not contribute significantly. Elemental sulfur and selenium oxidize P5 with high preference to yield P5-thio- and P5-seleno-P5-deltacyclenes 10 and 11 of the intact cages again. Longer reaction time and more than stoichiometric amounts of selenium, leads to tri-seleno-P5-tetracycloundecane 12, a partially opened oxidized rearrangement product. The ligand properties of racemic 9a were determined. Diphosphetane phosphorus atom P2 of 9a is the active donor center to bind a Cr(CO)5 fragment, but a tautomerization of 9a takes place if [(benzene)RuCl2]2 is added. A hydrogen atom migrates from P1 to the oxygen atom to form a phosphinous acid ligand. The lone pair of P1 is regenerated and acts as the active ligand function of the cage in this case. As for 5, the base n-BuLi induces an efficient cage rearrangement reaction of 9a, where P1 and the neighboring carbon atom C4 containing its t-Bu substituent change places. C4 moves to its new position without breaking the bond with P5, this way forming the novel P1-oxo-P5-norsnoutene cage in a highly diastereoselective process.

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