Sep 2021 News Awesome and Easy Science Experiments about Dichloro(benzene)ruthenium(II) dimer

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The intermolecular dehydrogenative coupling of 1,1,1,3,5,5,5- heptamethyltrisiloxane with aromatic compounds such as aryloxazolines and arylimines in the presence of a catalytic amount of [RuCl2(p-cymene)] 2 gave the corresponding orthosilylated products in good yields.

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

Sep 2021 News Extended knowledge of Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II)

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New bichromophoric di- and trinuclear complexes were synthesized through coordinate strapping of one or two (bpy)2RuII/(phen)2RuII/Cp(PP h3)RuII moieties to [Zn{(MeS)8TAP}] 1, core. Thus five new complexes of the type [Zn{(MeS)8TAP}{Ru(bpy)2}][PF6] 2 2, bent and linear [Zn{(MeS)8TAP}{Ru(bpy)2}{Ru(phen)2}][PF 6]4 3 and 4, bent and linear [Zn{(MeS)8TAP}{Ru(bpy)2}{RuCp(PPh3)}][P F6]3 5 and 6, were synthesized and characterized using IR, 1H NMR, UV-visible, and mass spectral data. The trinuclear complexes 3-6 possessed bent (kappa4-S2,S3,S7,S 8)[RuII]2 and linear (kappa4-S2,S3,S12,S13 )[RuII]2 arrangements of the peripheral metallo-chromophore units. Unlike the two reversible reduction waves in complex 1 observed at E1/2 -0.34 and -0.60 V, only one reversible reduction wave was observed, between E1/2 -0.56 to -0.58 V vs. Ag/AgCl, in the di- and trinuclear complexes 2-6. Also in the anodic scans, the dinuclear complexes 2, as well as linear trinuclear complexes 4 and 6, exhibited two successive one electron oxidations, the first at E1/2 ? 0.62 V due to Ru(II)/Ru(III) process and second at E1/2 ? 1.16 V vs. Ag/AgCl due to {(MeS)8TAP}/{(MeS)8TAP}+ processes, while the bent trinuclear complexes 3 and 5 exhibited three successive one electron oxidations, i.e. one additional oxidation wave at E1/2 0.88 and 0.90 V vs. Ag/AgCl, respectively. In the fluorescence measurements, Soret excitation led to strong [Zn{(MeS)8TAP}] centered S2 emission together with a rapid intercomponent excitation energy transfer (k 107-108 s-1) to peripheral Ru(II) unit that showed emission maxima between 535 and 545 nm. Lifetime analysis showed that Ru(II)* emission predominated in the dinuclear complex 2, but its contribution dropped significantly upon formation of the trinuclear complexes, which has been explained in terms of relative variation of the LUMO energies of the linked chromophores in the excited states.

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

Sep 2021 News Can You Really Do Chemisty Experiments About Dichloro(benzene)ruthenium(II) dimer

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The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.37366-09-9, Name is Dichloro(benzene)ruthenium(II) dimer, molecular formula is C12H12Cl4Ru2. In a Article,once mentioned of 37366-09-9, Product Details of 37366-09-9

Reaction of the dimers [RuCl2(arene)]2 (arene = benzene, p-cymene, mesitylene) with bis(oxazolines) (N-N = bis(2-oxazoline) (box), 2,2-bis(2-oxazolinyl)propane (bop), 1,2-bis(2-oxazolinyl)benzene (benbox)) in the presence of NaSbF6 gives the complexes [RuCl(N-N)(arene)][SbF6] (1-8), which have been fully characterized. Treatment of these cations with AgSbF6 generates dications which in some cases are enantioselective catalysts for Diels-Alder reaction of methacrolein and cyclopentadiene. Two complexes, [RuCl(iPr-benbox)(p-cymene)][SbF6] (5) and [Ru(OH2)(iPr-bop)(mes)][SbF6]2 (10; mes = mesitylene), have been characterized 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

Sep 2021 News Some scientific research about Cis-Dichlorobis(2,2′-bipyridine)ruthenium(II)

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The mononuclear [Ru(bpy)2(bpym)][PF6]2 complex (bpy = 2,2?-bipyridine; bpym = 2,2?-bipyrimidine) has been prepared in its enantiopure Lambda form. Because of the chelating property of the bipyrimidine moiety, it is possible to use this chiral-at-metal complex as a chiral inorganic ligand for a second metal cation acting as a catalytic center. Here we report the synthesis and the structural characterization of a novel dinuclear Lambda-[(bpy)2Ru(bpym)RuCl(p-cymene)]3+ compound (1). The asymmetric-inducing properties of the enantiopure chiral-at-metal metalloligand have been probed during asymmetric transfer hydrogenation to ketones catalyzed by 1. This provides one of the very few illustrations of the potential of this original class of chiral inorganic ligands.

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

Sep 2021 News Extended knowledge of Ruthenium(III) chloride hydrate

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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. 20759-14-2, Name is Ruthenium(III) chloride hydrate, molecular formula is Cl3H2ORu. In a Article,once mentioned of 20759-14-2, Product Details of 20759-14-2

trans-[(dppm)2ClRu=C(CH2)3O]+ (2) (dppm=Ph2PCH2PPh2) and trans-[(dppm)2ClRu=C(CH2)2CH(CH) 3O]+ (3) cations were obtained from the reaction of cis-[RuCl2(dppm)2] (1) with 3-butyn-1-ol and 4-pentyn-2-ol, respectively. cis-Dichlororuthenim complex [RuCl2((dppene)(bpy)] (4) (dppene=Ph2PCHCHPPh2, bpy=2,2?-bipyridyl) also reacts with terminal alkynes e.g. 4-pentyn-2-ol and phenylacetylene to give cis-chloro-(oxycarbene)[(dppene)(bpy)ClRu=C(CH2)2CH (CH)3O]+ (5) and cis-chloro-(vinylidene)[(dppene)(bpy)ClRu=C=CHPh]+ (6) cations. cis-[RuCl2(bpy)2] (7) also react with 4-pentyn-2-ol to give dioxacyclic carbene dication cis-[(bpy)2Ru=(C(CH2)2CH(CH)3O) 2]2+ (8). In the reaction of RuCl2(PPh3)3 (9) with 3-butyn-1-ol the dimer [(PPh3)2ClRu=C(CH2)3O] 2 2+ (10) was obtained. The new synthesis method of 1 and cis-[RuCl2(dppm)2]·2MeOH (1a) is also presented. These complexes have been fully characterized by IR, 1H, 13C{H} and 31P{H} NMR) and single crystal X-ray diffraction for 2, 3, 5 and 1a. The catalytic activity of 10 in reactions of ROMP of norbornene was also studied.

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

Sep 2021 News The Absolute Best Science Experiment for Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II)

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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. 32993-05-8, Name is Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II), molecular formula is C41H35ClP2Ru. In a Article,once mentioned of 32993-05-8, Product Details of 32993-05-8

Ruthenium compounds of general formula Cp?RuX(PR2R?) 2 (Cp? = eta5-C5H5 (Cp), eta5-C9H7 (Ind), eta5C 5(CH3)5 (Cp*); X = Cl, CF 3C(O)O; R = C6H5 (Ph), C6H 4(CH3) (m-tolyl); R? = C6H5, C6H11 (Cy), C6H4(CH3) (m-tolyl, o-tolyl)) are examined as catalysts for the aldehyde olefination starting from diazo compounds, phosphanes, and aldehydes. Cp*RuCl(PPh 3)2 is highly active for the olefmation of several aldehydes, displaying a very high E-selectivity, as well as for ketone olefination (with benzoic acid as cocatalyst). The reaction’s mechanism is substantiated by the isolation of a catalytic active reaction species, namely, a mixed carbene/phosphane ruthenium complex, Cp*RuCl(=CHCO 2Et)(PPh3) (8). Spectroscopic studies reveal that the latter compound reacts with PPh3 to produce the phosphorus ylide Ph3P=CHCO2Et, which further reacts with the aldehyde to produce the olefin.

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

10-Sep-2021 News Final Thoughts on Chemistry for Dichloro(benzene)ruthenium(II) dimer

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The mononuclear cations of the general formula [(eta6-arene)RuCl(pdpt)]+ (pdpt = 5,6-diphenyl-3-(pyridine-2-yl)-1,2,4-triazine; arene = C6H6 (1); C6H5Me (2); p-PriC6H4Me (3); C6Me6 (4)) have been synthesised from 5,6-diphenyl-3-(pyridine-2-yl)-1,2,4-triazine (pdpt) and the corresponding chloro complexes [(eta6-C6H6)Ru(mu-Cl)Cl]2, [(eta6-C6H5Me)Ru(mu-Cl)Cl]2, [(eta6p-PriC6H4Me)Ru(mu-Cl)Cl]2 and [(eta6-C6Me6)Ru(mu-Cl)Cl]2, respectively. The X-ray crystal structure analyses of [1][PF6] · (C6H6)2.5 and [2][PF6] · (CH3CN)2 reveal a typical piano-stool geometry around the metal centre and in the crystal packing a complexed networks of intermolecular interactions.

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

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

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In order to gain a deeper mechanistic understanding of water oxidation by [(bda)Ru(L)2] catalysts (bdaH2 = [2,2?-bipyridine]-6,6?-dicarboxylic acid; L = pyridine-type ligand), a series of modified catalysts with one and two trifluoromethyl groups in the 4 position of the bda2- ligand was synthesized and studied using stopped-flow kinetics. The additional -CF3 groups increased the oxidation potentials for the catalysts and enhanced the rate of electrocatalytic water oxidation at low pH. Stopped-flow measurements of cerium(IV)-driven water oxidation at pH 1 revealed two distinct kinetic regimes depending on catalyst concentration. At relatively high catalyst concentration (ca. ?10-4 M), the rate-determining step (RDS) was a proton-coupled oxidation of the catalyst by cerium(IV) with direct kinetic isotope effects (KIE > 1). At low catalyst concentration (ca. ?10-6 M), the RDS was a bimolecular step with kH/kD ? 0.8. The results support a catalytic mechanism involving coupling of two catalyst molecules. The rate constants for both RDSs were determined for all six catalysts studied. The presence of -CF3 groups had inverse effects on the two steps, with the oxidation step being fastest for the unsubstituted complexes and the bimolecular step being faster for the most electron-deficient complexes. Though the axial ligands studied here did not significantly affect the oxidation potentials of the catalysts, the nature of the ligand was found to be important not only in the bimolecular step but also in facilitating electron transfer from the metal center to the sacrificial oxidant.

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

10-Sep-2021 News Properties and Exciting Facts About (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium

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The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.246047-72-3, Name is (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium, molecular formula is C46H65Cl2N2PRu. In a Patent,once mentioned of 246047-72-3, Recommanded Product: 246047-72-3

The invention relates to a process for the preparation of bidentate Schiff base catalysts containing a salicylaldimine-type ligand.

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

10-Sep-2021 News New explortion of Benzylidenebis(tricyclohexylphosphine)dichlororuthenium

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The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.172222-30-9, Name is Benzylidenebis(tricyclohexylphosphine)dichlororuthenium, molecular formula is C43H72Cl2P2Ru. In a Article,once mentioned of 172222-30-9, COA of Formula: C43H72Cl2P2Ru

Reactions of 5-norbornene-2-methanol with arene cyclopentadienyliron complexes led to the synthesis of two new classes of norbornene monomers with ether or ester bridges; ring-opening metathesis polymerization of these monomers using ruthenium-based catalysts gave rise to high molecular weight polymers displaying exceptional thermal stability.

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