Tag: M.W:700-800

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Thiazyl Chloride Complexes of Ruthenium(II)

The compound (NSCl)3 reacts with ruthenium(II) complexes of type (X=Cl, Br, CN, SCN, or SnCl3) an (pip=piperidine) to yield (X=Cl; X’=Cl, Br, CN, SCN, or SnCl3) and , respectively.The complexes have been characterized by elemental analyses, spectroscopic (i.r., 1H n.m.r., u.v.-visible) magnetic susceptibility, and t.l.c. data.

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

The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.92361-49-4, Name is Chloro(pentamethylcyclopentadienyl)bis(triphenylphosphine)ruthenium(II), molecular formula is C46H45ClP2Ru. In a Article£¬once mentioned of 92361-49-4, category: ruthenium-catalysts

H-C Bond Cleavage by (nu5-Cyclopentadienyl)bis(triorganylphosphine)ruthenium Organyl Complexes

Ruthenium(II) complexes of the type Cp(MenPh3-nP)2RuR with R = CH3, and R = CH2CMe3 have been prepared from the appropriate ruthenium chloride and alkyllithium or alkylmagnesium chloride.Of the methyl complexes having at least one phenyl group in the phosphane ligand, 17 reacts at 20 deg C and 14, 19, and 21 upon warming by intramolecular H-C(phenyl) bond cleavage and elimination of methane to give the ortho-metallated products Cp(MenPh3-nP) 15, 18, 20, and 22.The neopentyl ruthenium complexes 23, 25, 32, 34, and 36 react in an intermolecular manner with benzene by H-C(benzene) bond cleavage and elimination of neopentane to give the phenylruthenium compounds 24, 26, 33, 35, and 37.Whereas the Me3P-complex 36 as well as (C5H5)(Me3P)(Ph3P)RuCH2CMe3 (30) react with benzene to give neopentane and the phenyl complexes 37 and 31, the complexes 23, 25, 32, and 34 react to give undeuterated neopentane and the phenyl compounds 24, 26, 33, and 35.The phenyl complex 24 and the ruthenium compounds having benzyl (34) or p-tolyl groups (40) react with toluene to give an equilibrium mixture of the m- and p-tolyl complexes 38 and 40.H-C(arene) bond cleavage is also observed with other aromatic compounds such as phenyl bromide or naphthalene.In the case of 36 bond cleavage occurs selectively in the position meta to the substituent to give 42 and 43.Styrene, in contrast, reacts with 36 with cleavage of the vinylic 1(E)-H-C bond to give 44, while ethylene reacts to give the (nu2-ethylene)-vinylruthenium complex 45, which upon warming isomerizes with ethylene insertion into the vinyl-Ru bond to give the nu3-1-methylallyl compound 46. – In the H-C bond cleavage reaction, (C5Me5)Ru complexes are more reactive than the corresponding systems with a C5H5 group, and in both series the reactivity decreases with increasing basicity of the phosphine ligand. – The crystal structure analysis of Cp(Ph3P)(Me3P)RuCH2CMe=CH2 (13) is described.

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

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Comparison of Redox Activity between 2-Aminothioether and 2-Aminothiophenol: Redox-Induced Dimerization of 2-Aminothioether via C-C Coupling

Three chemical reactions of two 2-aminothioethers and 2-aminothiophenol with CpRuIICl(PPh3)2 (Cp- = cyclopentadienyl anion), under identical reaction conditions, are reported. While 2-(methylthio)aniline, H2L1 and an analogous substrate, 2-(phenylthio)aniline yielded dicationic dinuclear complexes [(PPh3)CpRuII(L3/L4)RuIICp(PPh3)]Cl2 (where L3 = (4E)-4-(4-imino-3-(methylthio)cyclohexa-2,5-dienylidene)-2-(methylthio)cyclohexa-2,5-dienimine ([1a]Cl2) and L4 = (4E)-4-(4-imino-3-(phenylthio)cyclohexa-2,5-dienylidene)-2-(phenylthio)cyclohexa-2,5-dienimine ([1b]Cl2)), the reaction with 2-aminothiophenol (H2L2) produced a mononuclear complex [(PPh3)CpRuII(L2)]Cl (where L2 = 6-iminocyclohexa-2,4-dienethione) ([2]Cl). All these complexes are obtained in high yields (65%-75%). Formations of the products from the above reactions involve a similar level of oxidation of the respective substrate, although their courses are completely different. A comparison between the above two chemical transformations are scrutinized thoroughly. Characterizations of these complexes were made using a host of physical methods: X-ray crystallography, nuclear magnetic resonance (NMR), cyclic voltammetry, ultraviolet-visible (UV-vis), electron paramagnetic resonance (EPR) spectroscopy, and density functional theory (DFT). The complexes [1a]Cl2 and [1b]Cl2 showed intense metal-to-ligand charge transfer transition in the long wavelength region of the spectrum, at 860 and 895 nm, respectively, and displayed two reversible electron transfer (ET) processes at [1a]2+: -0.28 and -0.52 V; [1b]2+: -0.13 and -0.47 V, along with an irreversible ET process at 0.76 and 0.54 V, respectively. The ET processes at negative potentials are due to successive reductions of the bridging ligand, which are characterized by EPR and UV-vis spectroscopy. The one-electron reduced compound, [1a]+, showed a intraligand charge transfer transition (ILCT) at 1530 nm. The complex [2]+ showed a reversible ET process at -0.36 V and two irreversible ET processes at -1.04 and 1.18 V, respectively. DFT calculations were used to support the spectral and redox properties of the complexes and also to throw light on the difference of redox behavior between thioether and thiophenol substrates. (Chemical Equation Presented).

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

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Half-Sandwich Ruthenium(II) Complexes as Catalysts for Stereoselective Carbene-Carbene Coupling Reactions

Cyclopentadienyl complexes of general formula [RuX(eta5-ligand)(PR3)2] have been found to catalyze the stereoselective decomposition of ethyl diazoacetate (EDA) to form diethyl maleate (DEM) in 95-99% purity with less than 1 mol % of catalyst, at temperatures depending on the bulkiness of the phosphine and the eta5-ligand as well as the nature of the anionic ligand X. A detailed study of the reaction between [RuCl(eta5-C5H5)(PPh3) 2] and EDA suggests that dissociation of one PPh3 is a key step of the catalytic process, which proceeds via the intermediate [RuCl(eta5-C5H5)(=CHCO 2Et)(PPh3)]. Although this electrophilic carbene was not detected in the reaction mixture, it was independently prepared in solution at low temperature starting from [Ru(eta2-02CMe)(eta5-C5H 5)(PPh3). The acetate reacts with EDA at -40C to form the cyclic ester [Ru(CH(CO2Et)OC(Me)O)(eta5-C5H 5)(PPh3), which on treatment with Me2SiCl2 gives the metal carbene postulated in the catalytic cycle. The stoichiometric reaction of the latter compound with EDA selectively affords the olefin derivative [RuCl-(eta5-C5H5)(eta 2-DEM)(PPh3)], which was also detected in the catalytic cycle. The new complexes [RuCl(eta5-C5H5)(PR3)2] (PR3 = PPh2(2-MeC6H4), PPh2Cy, P(3-MeC6H4)3), bearing phosphines bulkier than PPh3, have been prepared in high yield starting from ruthenium trichloride hydrate, cyclopentadiene, and phosphine in refluxing ethanol.

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

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Alkenylvinylidene and allenylidene complexes: Evidence for the formation of a metal-trienylidene intermediate

Reactions of [Ru(thf)(PPh3)2(eta-C5H5)][PF 6] with buta-1,4-diyne in the presence of nucleophiles give alkenylvinylidene or allenylidene complexes; the results are rationalised in terms of the formation of the intermediate trienylidene cation [Ru(C=C=C=CH2)-(PPh3)2(eta-C 5H5)]+ which undergoes nucleophilic addition at Cgamma; the X-ray structure of the heteroallenylidene [Ru{C=C=CMe(NPh2)}(PPh3)2(eta-C 5H5)][PF6] 2 is determined.

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

Related Products of 14564-35-3, Children learn through play, and they learn more than adults might expect. Science experiments are a great way to spark their curiosity, get their minds active, and encourage them to do something that doesn’t involve a screen. 14564-35-3, C38H34Cl2O2P2Ru. A document type is Article, introducing its new discovery.

Organometallic Lewis Acids, IL. – Bis(acyl)-Bridged Heterometallic Complexes of Rhenium, Molybdenum, Ruthenium, and Copper

The reaction of the metalla-beta-diketonate complex <(OC)4-Re<-C(Me)O>2> with various organometallic Lewis acids yields the bis(acyl)-bridged bimetallic complexes (OC)4-Re<-C(Me)O->2Re(CO)4 (1), (OC)4Re<-C(Me)O->2MoCp(CO)2 (2), (OC)4Re<-C(Me)O->2Ru(eta3-C3H5)(nbd) (nbd = norbornadiene) (3), <(OC)4Re<-C(Me)O->2Ru(PPh3)2(CO)2> (4) and (OC)4Re<-C(Me)O->2Re(CO)4 (5), respectively.The structures of the compound 1-5 have been determined by X-ray diffraction.They show different conformations of the six-membered ring Re<-C(Me)O->2.The molecular structure of complex 1 proves a “flipping” of the acyl ligands. Key Words: Bis(acyl)-bridged bimetallic complexes / Rhenium complexes / Molybdenum complex / Ruthenium complex / Copper complex

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

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

Alkynethiolato and alkyneselenolato ruthenium half-sandwich complexes: Synthesis, structures, and reactions with (eta5-C5H5)2Zr

Alkynethiolato and alkyneselenolato complexes of ruthenium, CpRu(PPh3)2(EC?CR) (Cp = eta5-C5H5; E = S, R = Ph (1a), SiMe3 (1b), tBu (1c); E = Se, R = Ph (2a), SiMe3 (2b)), were synthesized by the reactions of CpRuCl-(PPh3)2 with corresponding lithium alkynechalcogenolates in THF. An analogous reaction of Cp*RuCl(PEt3)2 (Cp* = eta5-C5Me5) with LiSC?CPh produced Cp*Ru(PEt3)2(SC?CPh) (3). Complexes 1a and 2a were allowed to react in THF with “Cp2Zr”, generated in situ from CP2ZrCl2 and 2 equiv of n-BuLi, from which the S-bridged Ru-Zr dinuclear complexes CpRu(PPh3)(C?CPh)(mu-S)ZrCp2 (4a) and CpRu(PPh3)(C?CPh)(mu-Se)ZrCp2 (4b) were isolated, respectively. In these complexes, C-S(Se) bond cleavage of the alkynechalcogenolate ligands was promoted by “Cp2Zr”, and the Zr atom was oxidized from II to IV. Treatment of 4a and 4b in THF under 1 atm CO gave rise to CpRu(CO)(C?CPh)(mu-E)ZrCp2 (E = S (5a), Se (5b)), while addition of tert-butyl isocyanide to a THF solution of 4b afforded CpRu(CNtBu)(C?CPh)(mu-Se)ZrCp2 (6). The crystal structures of 1a, 1c, 2a, 2b, 3, 4a, 4b, and 5b were determined by X-ray diffraction analysis.

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

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, Quality Control of: Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II)

Dihydrogen complexes of ruthenium. 2. Kinetic and thermodynamic considerations affecting product distribution

Cationic ruthenium dihydrogen complexes of the form [(eta-C5H5)Ru(L)(L?)(eta2-H 2)]BF4 (L = CO, L? = PCy3 (1a), PPh3 (2a), PMe2Ph (3a), PMe3 (4a) have been prepared by protonation of the corresponding neutral hydrides. Carbonyl free derivatives such as [(eta-C5H5)Ru(P P?)(eta2-H2)]BF4 (P P? = 1,2-bis(dimethylphosphino)ethane (dmpe) (5a), (1,1-dimethyl-2,2-diphenylphosphino)ethane (dmdppe) (6a), (R)-(+)-1,2-bis(diphenylphosphino)propane ((R)-prophos) (8a), bis(PPh3) (9a)) were similarly prepared. Pentamethylcyclopentadienyl analogues [(eta-C5Me5)Ru(P P?(eta2-H2)]BF4 (P P? = dmdppe (7a), (PPh3J2 (10a)) and [(eta-C5Me5)Ru(CO)(PCy3)(eta 2-H2)]BF4 (11a) have also been prepared. Identification of these species as dihydrogen complexes is based upon observation of substantial H-D coupling (22-32 Hz) in the 1H NMR spectra of the HD analogues, prepared by protonation of the corresponding deuterides. In every case studied in detail, the kinetic product of the protonation reaction is the dihydrogen complex, but an intramolecular isomerization occurs to give variable amounts of the transoid dihydride form at equilibrium. The composition of the equilibrium mixture and the rate at which the equilibrium is obtained depend upon the ligand environment. Facile rotation of the coordinated H2 ligand in the ruthenium complexes is established by the study of chiral complexes. The coordinated H2 in these complexes is substantially activated toward heterolytic cleavage. In the case of 5a, the measured pKa is 17.6 (CH3CN), with the dihydrogen form deprotonated more rapidly than the dihydride.

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

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eta1-Vinylidene formation from internal alkynones by C-C bond migration

The [mu2-N2(CpRu(PPh3)2) 2]2+ (12+) dication is a source of the formal 16-electron [CpRu(PPh3)2]+ fragment, and it reacts with internal alkynes such as 1,3-diphenylpropynone, 4-phenyl-3-butyn-2- one, and 3-cyclopropyl-1-phenylpropynone to yield eta1-vinylidene complexes 2a+-2c+ by C-C bond activation. In the case of 1,3-diphenylpropynone, the eta1-ketone complex [CpRu(PPh 3)2{PhC(eta1-O)C?CPh}]+ (3a+) was isolated as its PF6- salt, and it is apparently an intermediate in the formation of the vinylidene complex. Complexes 2a+-2c+ were characterized as their BArF 4- [ArF = 3,5-bis(trifluoromethyl)phenyl] salts by NMR and IR spectroscopic methods, ESI-MS, and EA. The single crystal X-ray diffraction structure of 2aBArF4 is presented. These reactions represent the first examples where an internal alkyne undergoes C-C bond migration to form an eta1-vinylidene complex. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.

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

Synthetic Route of 92361-49-4, Children learn through play, and they learn more than adults might expect. Science experiments are a great way to spark their curiosity, get their minds active, and encourage them to do something that doesn’t involve a screen. 92361-49-4, C46H45ClP2Ru. A document type is Review, introducing its new discovery.

Reaction of Cp*RuCl(PPh3)2 with dioxygen and formation of a neutral complex Cp*RuCl(O2)(PPh3)

Reaction of Cp*RuCl(PPh3)2 (1) with atmospheric oxygen occurs at room temperature in the presence of acetone or methylene chloride leading to Cp*RuCl(O2)(PPh3) (2). This complex is remarkably stable in the solid state and it can also release, under not unduly harsh conditions, the activated oxygen molecule, which can oxidize the phosphite L = MeOP[ (OCHMe)2CH2] to the corresponding phosphate, along with formation of the mono- and disubstituted Cp*RuCl (PPh3)(L) (5), Cp*RuCl(L)2 (6) and [Cp*RuCl(PPh3)(L)2]Cl (7), complexes. Structural information of phosphite derivatives 5 and 6 has been obtained by X-ray diffraction.

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