A new application about 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, category: ruthenium-catalysts

Our previously developed strategy of generating ketene intermediates via Ru-catalyzed intramolecular oxidation of terminal alkynes is applied to propargyl sulfoxides. The reaction undergoes interesting further rearrangement upon the ketene generation to afford alpha,beta-unsaturated thioesters in good to excellent yields in the reported cases.

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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 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, COA of Formula: C41H35ClP2Ru

Reaction of <(eta5-C5H5)Ru(PPh3)2Cl> (1) with sodium nitrite in hot acidified ethanol followed by anion exchange gave the red crystalline solid <(eta5-C5H5)Ru(PPh3)(NO)(Cl>PF6 (2) in good yield.Compound 2 has been crystallographically characterised and shows a large interligand angle at ruthenium between the chloride and nitrosyl ligands.The dication <<(eta5-C5H5)Ru(PPh3)(CNtBu)(NO)>2> (4) has been prepared from <(eta5-C5H5)Ru(PPh3)(CNtBu)(Cl)> (3) and nitrosonium tetrafluoroborate.

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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 syntheses of cationic ruthenium(II) allenylidene complexes [(1a-e)PF6] of the type [CpRu(=C=C=CR2)(PPh3)2]PF6 (1a, R2C: = cycloheptatrienylidene; 1b, R2C: = 2,7-dimethyl4,5-benzocycloheptatrienylidene; 1c, R2C: = 2,7-diphenyl-4,5-benzocycloheptatrienylidene; 1d, R2C: = dibenzo[a,e]cycloheptatrienylidene; 1e, R2C: = 4,5-dihydrodibenzo[a,e]cycloheptatrienylidene) are reported. In the series 1a-e, the decreasing ability of R2C: to stabilize a positive charge results in a tuning of the electronic and optical properties by changing the relative contributions of the two canonical forms [Ru+]=C=C=CR2 (A) and [Ru]-C=C-CR2+ (B), which is studied particularly by NMR and UV/visible spectroscopy. The first molecular hyperpolarizabilitiy beta of (1b)PF6 has been determined by hyper Raleigh scattering. The X-ray crystal structures of (1b)PF6, (1d)PF6·CH2Cl2, and the acetylide complex CpRu(C=C-C7H7-2,4,6)(PPh3)2 are presented.

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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 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, Safety of Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II)

The cationic mononuclear complexes [Ru(eta5-arene) (kappa2-dpp)(EPh3)]+ (eta5-arene = C5H5 (1), C5Me5 (2), C 9H7 (3); E=P (1a, 2, 3), As (1b); dpp = 2,3-bis(2-pyridyl) pyrazine) resulting from the reactions of [Ru(eta5-arene)(EPh 3)2Cl] with dpp in equimolar ratio in methanol under refluxing conditions, containing both group 15 donor and a planar polypyridyl ligand are reported here. These complexes have been isolated as their hexafluorophosphate salts and fully characterized by elemental analyses and spectral techniques, viz. IR, 1H and 31P NMR, FAB-MS and electronic spectral studies.

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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 ruthenium complex (eta5C5H5)(PPh3)2RuCl (1) catalyzes the addition of allylic alcohols to terminal alkynes, yielding beta,gamma-unsaturated ketones. The intermediacy of a ruthenium vinylidene complex is indicated by the synthesis of this proposed intermediate and the demonstration of the same reaction profile as with catalyst 1. Loss of terminal deuterium in labeled alkynes supports this conclusion. Ligand substitution studies demonstrate the necessity of phosphine loss and precoordination of the allylic alcohol. Deuterium labeling of allyl alcohol demonstrates that the two allylic termini do not become equivalent and that the olefin geometry does not scramble. In contrast to these observations, 3-buten-2-ol shows complete regioselectivity in the condensation but randomization of olefin geometry as determined by deuterium labeling. A cohesive mechanistic rationale accommodates these seemingly disparate observations.

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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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Treatment of [PdCl2(PhCN)2] with 1 equivalent of 2,3-bis(diphenylphosphino)propene (2,3-dpppn) in CH2Cl2 gave [PdCl2(2,3-dpppn)] 1 together with some [PdCl2(1,2-dpppn)] 2 [1,2-dpppn = cis-1,2-bis(diphenylphosphino)propene]. Treatment of 1 with an excess of benzylamine did not lead to addition to the double bond, but resulted in complete isomerisation to 2, as monitored by 31P-{1H} and 1H NMR spectroscopy. Metathesis of 2 with NaI in acetone gave [PdI2(1,2-dpppn)] 3. Platinum(II) complexes [PtCl2(2,3-dpppn)] 4 and [PtCl2(1,2-dpppn)] 5 were prepared and characterised analogously. Treatment of 2 or 5 with an excess of MeLi gave [PdMe2(1,2-dpppn)] 6 and [PtMe2(1,2-dpppn)] 7 respectively, and treatment of 5 with hydrazine hydrate and an excess of HC?CPh in ethanol gave [Pt(C?CPh)2(1,2-dpppn)] 8. Treatment of [PdCl2(PhCN)2] with 2 equivalents of AgBF4 and 2 equivalents of 2,3-dpppn gave a mixture of at least four isomeric complexes, probably cis- and trans-[Pd(2,3-dpppn)2][BF4]2 and cis- and trans-[Pd(1,2-dpppn)2][BF4]2. On treatment with benzylamine, this mixture was converted into a ca. 1:1 mixture of two isomers, which NMR spectroscopic evidence suggested were cis- and trans-[Pd(1,2-dpppn)2][BF4]2 9. Similarly, treatment of [Pt(Cl2(PhCN)2] with AgBF4-2,3-dpppn gave cis- and trans-[Pt(1,2-dpppn)2][BF4]2 10. A crystal structure determination was performed on the trans isomer, isolated on recrystallisation of the mixture from MeCN-Et2O. Treatment of [RuCl2(PPh3)3] with 2 equivalents of 2,3-dpppn gave a very insoluble complex, trans-[RuCl2(dpppn)2] 11. Treatment of [RuCl(eta5-C5H5)(PPh3) 2] with 2,3-dpppn in refluxing benzene gave [RuCl(eta5-C5H5)(1,2-dpppn)] 12. The formulation of 12 was confirmed by a single-crystal structure determination.

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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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Sequential reaction of the dimethylamino(trimethylsilylethynyljcarbene complexes [(CO)5M’=C(NMe2)CsCSiMe3] [M’ = W (1a), M’ = Cr (lb)] with KF/THF/MeOH, nBuLi and transition metal halides, [XMLn], affords heterobimetallic propynylidene complexes of the type [(CO)SM’=C(N-Me2)C=CMLn] [MLn= Ni(PPh3)Cp (4a, b), Ni(PMe2Ph)2-(Mes) (Mes = 2, 4, 6-C6H2Me3) (5a), Rh(CO)(PPh3)2 (6a), Fe(CO)2Cp (7a, b)]. In contrast, reaction of la with MeLi LiBr and [IFe(CO)2Cp] yields the novel N-metallated complex [(CO)2cP=C{N(Me)Fe(CO)2Cp)C=CSiMe3] (8a). The complexes [(CO)5M’=C(NMe2)C=CMLn] [MLn = Fe(CO)2Cp (7a, b), Ru(CO)2Cp (10a, b), Ru(CO)(PPh3)Cp (11a), Mn(CO)5 (12a), Re(CO)5 (13a)] are accessible by Pd-catalyzed coupling of the C-stannylated carbene complexes [(CO)SM’=C-(NMe2)C=CSnBu3] (9a, b) with [XMLn1. The related monomethylaminocarbene complexes [(CO)5M’=C(NHMe)C= CSnBu3] (16a, b), obtained by stannylation of [(CO)5M’=C(NHMe)C=CH] (15a, b) with Bu3SnNEt2, react with [IFe(CO)2Cp] to give the bimetallic complexes [(CO)5M’=C(NHMe)OCFe(CO)2Cp] (17a, b). The complexes 4a, 5a, 7a and 10a were characterized by X-ray structural analyses. The spectroscopic and structural data suggest that the two metal centers in 4-7, 10-13 and 17 interact only weakly. VCH Verlagsgesellschaft mbH.

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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 present invention relates to can be used as pharmaceutical intermediates shown in a following formula (III) diaryl-substituted imidazoles synthetic method, said method comprising: in the organic solvent, in catalyst, organic ligand and the presence of acid promoter, the following formula (I) compound, the compound of formula (II) compounds and radical reaction, after-treatment after reaction, so as to obtain the compound of said formula (III), wherein R 1, R 2 each independently selected from H, C 1-C 6 alkyl, C 1-C 6 alkoxy or halogen; X is halogen. The method adopts the specific reaction substrate, and through the catalyst, organic ligand, acidic promoter and organic solvent and in the comprehensive selective, thus can yield to obtain the target product, the imidazole compound of this kind the successful preparation, optimizes a synthesis process, improving the product yield, is very favorable to the large-scale production, has a broad market application prospect. (by machine translation)

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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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Two homo-trinuclear complexes [{(eta5-C5Me5)RhCl}3(mu3-L)] (1) and [{(eta5-C5H5)Ru(PPh3)}3(mu3-L)] (2) (H3L = 2,4,6-trimercapto-1,3,5-triazine) are reported. Both the complexes have been fully characterized by elemental analyses, FAB-MS, IR, NMR, electronic and emission spectral techniques. Molecular structure of 1 has been authenticated by single crystal X-ray diffraction analyses. Complex 1 revealed the strong intra- and inter-molecular C-H?X (X = Cl, pi) and pi-pi stacking interactions, which play important roles to stabilize crystal space packing. Furthermore, the pi-pi interactions in 1 lead to a double-helical motif.

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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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Reactions between <(L2 = 1,2-bis(diphenylphosphino)ethane (dppe) and 1,2-bis(phenylphosphino)methane (dppm)>, and 1-ethynylpyrene , in the presence of NH4PF6, NaBF4 or NaBPh4, have given the corresponding cationic eta’-vinylidene complexes.These cations are readily deprotonated to give the corresponding eta’-ethynyl complexes.They have been characterised on the basis of elemental analyses and spectroscopic studies.The cationic and neutral products have been further treated with methanol and higher alcohols and the resulting products characterised.

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