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It was surprisingly found that the highly active allyl alcohol redox isomerization catalyst [RuCp(PPh3)2](OTs) upon addition of a catalytic amount of a strong acid can change its catalytic action fully to the selective O-allylation of phenols with allyl alcohol. High turnover numbers (75,000 based on phenol; 200,000 based on allyl alcohol) are reached, and the catalyst is very stable in the presence of substrate. Addition of triphenylphosphine to the reaction mixture does not lead to further stabilization of the catalyst; instead, the free phosphine is rapidly allylated, thereby consuming the acid, which deactivates the catalytic system for allylation reactions. This catalyst with monodentate phosphine ligands is superior in both activity and selectivity to similar catalysts with bidentate phosphine ligands. Apart from phenols, also thiophenol can be efficiently allylated to form allyl phenyl sulfide.

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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 and Easy Science Experiments about Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II)

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Aminoboranes, H2BNRR?, represent the monomeric building blocks from which novel polymeric materials can be constructed via metal-mediated processes. The fundamental capabilities of these compounds to interact with metal centers have been probed through the coordination of H 2BNCy2 at 16-electron [CpRu(PR3) 2]+ fragments. In contrast to the side-on binding of isoelectronic alkene donors, an alternative mono(sigma-BH) mode of aminoborane ligation is established for H2BNCy2, with binding energies only ?8 kcal mol-1 greater than those for analogous dinitrogen complexes. Variations in ground-state structure and exchange dynamics as a function of the phosphine ancillary ligand set are consistent with chemically significant back-bonding into an orbital of B-H sigma* character.

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

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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

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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

09/9/2021 News Extracurricular laboratory:new discovery of Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II)

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A formal intramolecular olefin metathesis process between the C=C double bond of a vinylidene ligand and a pendant vinyl group in several ruthenium complexes, each with a ferrocenyl group, is followed by an additional intramolecular C-C bond formation between a Cp ligand of the ferrocenyl substituent and the vinylidene ligand. The regioselectivity of the C-C bond formation reaction at either the substituted or the nonsubstituted Cp group of the ferrocenyl group is possibly influenced by a steric effect between the neighboring substituent near the ferrocenyl group and the phosphine ligand on the ruthenium metal center. The structure of one ruthenium complex resulting from such a C-C bond formation has been fully characterized by a single-crystal X-ray diffraction analysis.

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

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The construction of fluorocarbene ligands within the coordination sphere of transition metal complexes using sequential nucleophilic and electrophilic addition to a vinylidene complex is described. Reaction of [Ru(eta5-C5H5)(dppe)(CCPhF)][N(SO2Ph)2] with [NMe4]F results in nucleophilic attack of fluoride at the metal-bound carbon of the vinylidene ligand to give alkenyl complex [Ru(eta5-C5H5)(dppe)(-CFCFPh)]. Subsequent eletrophilic fluorination with N-fluorobenzenesulfonimide (NFSI) results in the formation of the fluorinated carbene complex [Ru(eta5-C5H5)(dppe)(CF-CHFPh)][N(SO2Ph)2]. The fluorocarbene complexes undergo rearrangement to liberate free fluorinated alkenes, a process governed by the choice of solvent and anion, representing a new metal-mediated route to fluorinated alkenes from alkynes.

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

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The reactant in an enzyme-catalyzed reaction is called a substrate. Enzyme inhibitors cause a decrease in the reaction rate of an enzyme-catalyzed reaction.I hope my blog about 32993-05-8 is helpful to your research., Recommanded Product: Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II)

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: Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II)

Studies examining the photochemical reactivity of CpRu(PPh 3)2Cl and CpRu(PPh3)2Me towards the two electron donor ligands PEt3, C2H4, DMSO, the CH bond activatable reagents tetrahydrofuran, toluene, and pyridine, and the SiH bond activatable reagents HSiEt3 and HSi(Me) 2CHCH2) are presented. Broadband UV irradiation of CpRu(PPh3)2Cl leads to the formation of mono-substitution products such as CpRu(PPh3)(PEt3)Cl which are inert to further photochemical reaction, although thermally bis-substituted products such as CpRu(PEt3)2Cl can be formed. Room temperature irradiation of the related complex CpRu(PPh3)2Me with L = PEt3, C2H4, and DMSO also produces CpRu(PPh3)(L)Me. However, when these reactions are followed by in situ laser irradiation (325 nm source) at low temperature, three solvent activated isomers (ortho, meta and para) of CpRu(PPh3) 2(C6H4Me) are detected in toluene in addition to eta1- and eta3-coordinated benzyl species. Furthermore, photolysis in THF leads to both the C-D bond activation product CpRu(PPh3)2(OC4D7) and the labile coordination complex CpRu(PPh3)(THF)Me. Now CH4 rather than CH3D is liberated which suggests the involvement of an orthometallated species. The photochemically driven reaction of CpRu(PPh 3)2Me with HSiEt3 at 198 K generates CpRu(kappa2-2-C6H4PPh2)(SiEt 3)H and thereby confirms a role for an orthometallated complex is this process. Irradiation in cyclohexane produces the known orthometallated complex, CpRu(kappa2-2-C6H4PPh 2)(PPh3), and CH4 in accordance with this reactivity. The Royal Society of Chemistry 2014.

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

09/9/2021 News New explortion of Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II)

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32993-05-8, Name is Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II), molecular formula is C41H35ClP2Ru, belongs to ruthenium-catalysts compound, is a common compound. In a patnet, once mentioned the new application about 32993-05-8, Product Details of 32993-05-8

Systems of the type [(p-cym)Ru(PR3)(H)(H2BN iPr2)]+ (R = Cy, Ph) can be synthesized from (p-cym)Ru(PR3)Cl2 and H2BNiPr 2/Na[BArf4] and are best formulated as (hydrido)ruthenium kappa1-aminoborane complexes. VT-NMR measurements have been used to probe the sigma-bond metathesis process leading to Ru-H/H-B exchange, yielding an activation barrier of DeltaG ? = 7.5 kcal mol-1 at 161 K. Moreover, in contrast to the case for related non-hydride-containing systems, reactivity toward alkenes constitutes a viable route to a metal borylene complex via sacrificial hydrogenation.

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

9-Sep-2021 News Extracurricular laboratory:new discovery of Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II)

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Double nucleophilic aromatic substitution reactions between N-substituted (eta6-1,2-dichlorobenzene)RuCp+ salts and substituted 1,2-benzenediols have been carried out under mild conditions to prepare N-substituted (eta6-dibenzo[b,e][1,4]dioxin)ruthenium(II) complexes. The dibenzodioxin ligands were subsequently liberated by photolysis, with radiation from a sunlamp or from a medium pressure Hg lamp (300 nm).

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

Sep 2021 News Extracurricular laboratory:new discovery of Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II)

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The catalytic activity of the bis(allyl)-ruthenium(IV) dimer [{Ru(eta3:eta3-C10H16)(mu-Cl) Cl}2] (C10H16 = 2,7-dimethylocta-2,6-diene-1,8- diyl) (1), and that of its mononuclear derivatives [Ru(eta3: eta3-C10H16)Cl2(L)] (L = CO, PR3, CNR, NCR) (2) and [Ru(eta3:eta3-C 10H16)Cl(NCMe)2][SbF6] (3), in the redox isomerization of allylic alcohols into carbonyl compounds, both in tetrahydrofuran and in water, is reported. In particular, a variety of allylic alcohols have been quantitatively isomerized using [{Ru(eta3: eta3-C10H16)(mu-Cl)Cl}2] (1) as catalyst, the reactions proceeding in all cases faster in water. Remarkably, complex 1 has been found to be the most efficient catalyst reported to date for this particular transformation, leading to TOF and TON values up to 62 500 h-1 and 1 500 000, respectively. Moreover, catalyst 1 can be recycled and is capable of performing allylic alcohol isomerizations even in the presence of conjugated dienes, which are known to be strong poisons in isomerization catalysis. On the basis of both experimental data and theoretical calculations (DFT), a complete catalytic cycle for the isomerization of 2-propen-1-ol into propenal is described. The potential energy surfaces of the cycle have been explored at the B3LYP/6-311+G(d,p)//B3LYP/6-31G(d,p) + LAN2DZ level. The proposed mechanism involves the coordination of the oxygen atom of the allylic alcohol to the metal. The DFT energy profile is consistent with the experimental observation that the reaction only proceeds under heating. Calculations predict the catalytic cycle to be strongly exergonic, in full agreement with the high yields experimentally observed.

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