17-Sep-21 News Extracurricular laboratory:new discovery of Dichloro(benzene)ruthenium(II) dimer

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Ruthenium complexes of formula [(eta6-arene)Ru(LL*)- (H2O)][SbF6]2 (arene = C6H 6, p-MeC6H4iPr, C6Me6; LL* = bidentate chelate chiral ligand with PN, PP or NN donor atoms) have been tested as catalyst precursors for the asymmetric 1,3-dipolar cycloaddition of nitrones to methacrolein. The reaction occurs quantitatively with perfect endo selectivity and moderate enantioselectivity (up to 74 % ee). The ruthenium aqua complexes can be prepared from the corresponding chlorides, [(eta6-arene)RuCl(LL*)][SbF6]. Dipolarophile intermediates [(eta6-arene)Ru(PNiPr)(methacrolein)][SbF 6]2 (PNiPr = (4S)-2-(2-diphenylphosphanylphenyl)-4- isopropyl-1,3-oxazoline) as well as nitrone-containing complexes [(p-Me-C 6H4iPr)Ru(PNiPr)(nitrone)][SbF6]2 (nitrone = N-benzylidenephenylamine N-oxide, N-benzylidenemethylamine N-oxide, 3,4-dihydroisoquinoline N-oxide) have been also isolated and characterised. The crystal structures of the chlorides (RRu)-[(eta6-C 6Me6)RuCl(PNiPr)][SbF6], (RRu)- [eta6-C6H6)-RuCl(PNInd)][SbF6] {PNInd = (3aR,8aS)-2-[2-(diphenylphosphanyl)phenyl]-3a,8a-dihydroindane[1,2-d] oxazole} and those of the aqua solvates (RRu)-[(eta6- arene)Ru(PNiPr)-(H2O)][SbF6]2 (arene = C 6H6, C6Me6) were determined by X-ray diffraction methods. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.

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

9/17 News Can You Really Do Chemisty Experiments About Dichloro(benzene)ruthenium(II) dimer

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Dinuclear dichloro complexes [Ru(C6H6)Cl 2]2, [Ru(p-MeC6H4 iPr)Cl2]2, [Ru(1,2,4,5-C6H 2Me4)Cl2]2, and [Ru(C 6Me6)Cl2]2 react in ethanol with p-bromothiophenol to give the corresponding cationic complexes [Ru 2(C6H6)2(p-S-C6H 4-Br)3]+ (1), [Ru2(p-MeC 6H4iPr)2(p-S-C6H 4-Br)3]+ (2), [Ru2(1,2,4,5-C 6H2Me4)2(p-S-C6H 4-Br)3]+ (3), and [Ru2(C 6Me6)2(p-S-C6H4-Br) 3]+ (4), which can be isolated in quantitative yield as their chloride salts. X-ray structure analysis of these complexes shows that the nature of the arene ligand influences the folding of the p-S-C 6H4-Br units. In 1, where the less hindered arene ligand is present, the three phenyl rings of the thiolato units are not constrained to a coplanar arrangement, whereas in 4 the C6Me6 forces the three phenyl rings to be in perfect planarity. Complexes 2 and 3 show an intermediary arrangement.

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

16-Sep-21 News The Absolute Best Science Experiment for Dichloro(benzene)ruthenium(II) dimer

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Efficacy of the ferrocene appended piano-stool dipyrrinato complexes [(eta6-C6H6)RuCl(fcdpm)] (1), [(eta6-C10H14)RuCl(fcdpm)] (2), [(eta6-C12H18)RuCl(fcdpm)] (3) [(eta5-C5Me5)RhCl(fcdpm)] (4) and [(eta5-C5Me5)IrCl(fcdpm)] (5) [fcdpm = 5-ferrocenyldipyrromethene] toward anticancer activity have been described. Binding of the complexes with calf thymus DNA (CT-DNA) and BSA (bovine serum albumin) have been thoroughly investigated by UV-Vis and fluorescence spectroscopy. Binding constants for 1-5 (range, 104-105 M-1) validated their efficient binding with CT-DNA. Molecular docking studies revealed interaction through minor groove of the DNA, on the other hand these also interact through hydrophobic residues of the protein, particularly cavity in the subdomain IIA. In vitro anticancer activity have been scrutinized by MTT assay, acridine orange/ethidium bromide (AO/EtBr) fluorescence staining, and DNA ladder (fragmentation) assay against Dalton’s Lymphoma (DL) cells. Present study revealed that rhodium complex (4) is more effective relative to ruthenium (1-3) and iridium (5) complexes.

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

Sep-21 News The important role of Dichloro(benzene)ruthenium(II) dimer

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A family of chiral diphosphanes with systematically tunable electronic and steric properties have been used in the asymmetric hydrogenation of beta-aryl ketoesters with excellent ee values (up to 99.8%) by taking advantage of remarkable 4,4?-substituent effects on binap. These highly enantioselective Ru catalysts have also been effectively immobilized in room-temperature ionic liquids (RTIL).

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

Sep-21 News Discovery of Dichloro(benzene)ruthenium(II) dimer

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The reactions of [RuHCl(CO)(PPh3)3] and [(C6H6)RuCl2]2 with 2-benzoylpyridine have been examined, and two novel ruthenium(II) complexes – [RuCl(CO)(PPh3)2(C5H4NCOO)] and [RuCl2(C12H9NO)2] – have been obtained. The compounds have been studied by IR and UV-Vis spectroscopy, and X-ray crystallography. The molecular orbital diagrams of the complexes have been calculated with the density functional theory (DFT) method. The spin-allowed singlet-singlet electronic transitions of the compounds have been calculated with the time-dependent DFT method, and the UV-Vis spectra of the compounds have been discussed on this basis.

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

15-Sep-21 News Discovery of Dichloro(benzene)ruthenium(II) dimer

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The cyclopalladation of 3,5-bis(diphenylphosphinothioyl)pyridine afforded new kappa3S,C,S-pincer palladium complexes with a sigma-bond between Pd and 4C of the centered 3,5-pyridinediyl unit. By utilizing the quaternization and complexation ability of the pyridine imine nitrogen (Npy) atom, various new pincer-type complexes, including hetero-binuclear complexes, have been synthesized.

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

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

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Hetero-bimetallic polyhydride clusters exhibit a regio- and chemoselective activation of a substrate. The rational synthetic method for hetero-bimetallic polyhydride complexes using readily available halide complexes is reported. The reaction of hetero-bimetallic Ru-Ir trichloride complex, Cp?Ru(mu-Cl)3IrCp?(5a), in 2-propanol in the presence of a base afforded Cp?Ru(mu-H)3IrCp?(6a) by sequential salt metathesis and beta-hydrogen elimination. CpsRu(mu-H)3ML [Cps = Cp?, Cp?; ML = IrCp?, RhCp?, Ru(p-cymene), Ru(benzene)] were also selectively synthesized by reacting a mixture of CpsRuCl/n and [LM(mu-Cl)Cl]2 via the formation of CpsRu(mu-Cl)3ML. The IrCp?, RhCp?, and Ru(arene) complexes, Cp?Ru(mu-H)3IrCp?(6b), Cp?Ru(mu-H)3RhCp?(8), and Cp?Ru(mu-H)3Ru(arene) (10), were newly synthesized by this method. The reaction mechanism was discussed based on the hetero-bimetallic chloro-hydride intermediates. Absence of main group hydride reagents was responsible for maintaining the hetero-bimetallic structure during the introduction of the hydride ligand, which lead to selective formation of dinuclear mixed-metal trihydride-bridged complexes.

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

15-Sep-21 News Discovery of Dichloro(benzene)ruthenium(II) dimer

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The dinuclear RuII arene complexes [{(eta6-arene) RuCl}2(mu-2,3-dpp)](PF6)2, arene = indan (1), benzene (2), p-cymene (3), or hexamethylbenzene (4) and 2,3-dpp = 2,3-bis(2-pyridyl)pyrazine, have been synthesized and characterized. Upon irradiation with UVA light, complexes 1 and 2 readily underwent arene loss, while complexes 3 and 4 did not. The photochemistry of 1 was studied in detail. In the X-ray structure of [{(eta6-indan)RuCl}2(mu-2,3- dpp)](PF6)2 (1), 2,3-dpp bridges two RuII centers 6.8529(6) A apart. In water, aquation of 1 in the dark occurs with replacement of chloride with biexponential kinetics and decay constants of 100 ± 1 min-1 and 580 ± 11 min-1. This aquation was suppressed by 0.1 M NaCl. UV or visible irradiation of 1 in aqueous or methanolic solution led to arene loss. The fluorescence of the unbound arene is ?40 times greater than when it is complexed. Irradiation of 1 also had a significant effect on its interactions with DNA. The DNA binding of 1 is increased after irradiation. The non-irradiated form of 1 preferentially formed DNA adducts that only weakly blocked RNA polymerase, while irradiation of 1 transformed the adducts into stronger blocks for RNA polymerase. The efficiency of irradiated 1 to form DNA interstrand cross-links was slightly greater than that of cisplatin in both 10 mM NaClO4 and 0.1 M NaCl. In contrast, the interstrand cross-linking efficiency of non-irradiated 1 in 10 mM NaClO 4 was relatively low. An intermediate amount of cross-linking was observed when the sample of DNA already modified by non-irradiated 1 was irradiated. DNA unwinding measurements supported the conclusion that both mono- and bifunctional adducts with DNA can form. These results show that photoactivation of dinuclear RuII arene complexes can simultaneously produce a highly reactive ruthenium species that can bind to DNA and a fluorescent marker (the free arene). Importantly, the mechanism of photoreactivity is also independent of oxygen. These complexes, therefore, have the potential to combine both photoinduced cell death and fluorescence imaging of the location and efficiency of the photoactivation process.

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

14/9/2021 News Awesome Chemistry Experiments For Dichloro(benzene)ruthenium(II) dimer

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Eight amino alcohol-modified beta-CDs CD-1-CD-8 have been synthesized in acceptable yields and were employed to form artificial metalloenzymes with [RuCl2(Benzene)]2 and [RuCl2(Mesitylene)] 2, respectively. All the conformations of CD-1-CD-8, the complexes between CD-1-CD-8 and [RuCl2(Arene)]2, and the inclusion complexes between CD-1-CD-8 and acetophenone were characterized by UV, 1H NMR, 1H ROESY NMR, and quantum calculation. The catalytic activity of the formed artificial metalloenzymes in the asymmetric hydrogenation of aromatic ketones, especially the effect of the aromatic ligands’ volume on the enantioselectivity were investigated in detail, in which it was obvious that the enantioselectivity increased as the increase in the aromatic ligands’ volume. For the best artificial metalloenzyme constructed from the complex between CD-8 and [RuCl2(Mesitylene)]2, which not only exhibits a good tolerance to a wide range of substrates but also demonstrates some substrate selectivity, 76.39% ee was obtained for acetophenone and 79.67% ee for 2-acetylnaphthalene. A strategy to improve the enantioselectivity in the asymmetric reactions catalyzed by the artificial metalloenzymes based on CDs has been provided.

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

14-Sep-2021 News Awesome Chemistry Experiments For Dichloro(benzene)ruthenium(II) dimer

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(eta6-C6H6)(eta6-[3 n]Cyclophane)Ru(II) [BF4]2 and corresponding Os(II) [PF6]2, as well as bis(eta5-C5H5)(eta6,eta 6-[3n]cyclophane)Fe(II)Fe(II) [PF6]2 ([3n]cyclophane = [32](1,4)cyclophane 2, [33](1,3,5)cyclophane 3, [34](1,2,3,5)cyclophane 4, [34](1,2,4,5)cyclophane 5) have been synthesized and characterized. The complexation shifts of the 1H-NMR signals of the metal-bound aromatic protons (Hb) are ca. 0.5-0.7 and 0.1-0.4 ppm for Fe(II) and Ru(II) complexes, respectively, whereas those of Os(II) complexes are ca. -0.2-0.1 ppm. The complexation shifts of the 13C-NMR signals of the tertiary aromatic carbons of the metal-bound benzene ring are ca. 39-42 and 45-50 ppm for Ru(II) and Os(II) complexes, respectively. Thus the 1H- and 13C-NMR chemical shifts of the metal-bound aromatic hydrogens and carbons are strongly influenced by the anisotropy effect of the metal. The Ru(II) complexes showed electrochemically reversible responses. In the case of Os(II) complexes, a well-defined cathodic peak was also observed, but the rising portion of the corresponding anodic peak was somewhat deviated from the ordinary CV profile. In both cases, the redox process was attributed to the two-electron one-step mechanism, M(II) ? M(0) (M = Ru and Os). An analysis of the redox properties of the Ru(II) and Os(II) complexes suggested that the Os(II)[34](1,2,4,5)cyclophane complex would be the most suitable subunit of an anticipated one-dimensional organometallic polymer.

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