Tag: M.W:700-800

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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

Novel platinum group metal complexes bearing bidentate chelating pyrimidyl-NHC and pyrimidyl imidazolyl-thione ligands: Syntheses, spectral and structural characterization

A family of novel platinum group metal complexes containing bidentate chelating 1-pyrimidyl-3-methylimidazolyl bromide (HL1¡¤Br) and 1-pyrimidyl-3-methylimidazolyl-2-thione (L2) ligands has been synthesized. The synthetic protocol for the formation of these complexes differs from one ligand to the other. Treatment of ligand (HL1¡¤Br) with the metal precursors led to the formation of complexes via in situ carbene transfer reactions. The silver-NHC complex (1) was formed by the reaction of HL1¡¤Br with silver oxide under light-free conditions. Subsequent addition of appropriate metal precursors to the silver-NHC complex yielded [(eta6-arene)Ru(L1)Cl] PF6 complexes {arene = C6H6 (2), p- iPrC6H4Me (3), C6Me6 (4)} on stirring at room temperature, whereas the complexes [CpRu(L1)(PPh 3)]PF6 {Cp = C5H5 (5), C 9H7 (6)} were obtained under reflux conditions. In the case of ligand L2, stirring of equimolar quantities of metal precursors and the ligand at room temperature yielded [(eta6-arene)Ru(L2)Cl]PF 6 {arene = C6H6 (7), p-iPrC 6H4Me (8), C6Me6 (9)}, and [Cp*M(L2)Cl]PF6 {Cp* = C5Me5, M = Rh (10), Ir (11)}. All these complexes were characterized by CHN analysis, IR, NMR and mass spectrometry besides confirmation by single crystal X-ray diffraction studies for some representative complexes as their hexafluorophosphate salts [3]PF6, [5]PF6, [8]PF 6 and [10]PF6.

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

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The Syntheses and Crystal Structures of some Ten-vertex (MCB8; M=Ru or Os) Metallacarbaboranes: 9,9,9-(CO)(PPh3)2-nido-9,6-MCB8H10-5-(PPh3)> (M=Ru or Os) and <9,9,9-(eta-C5H5)(H)(PPh3)-arachno-9,6-RuCB8H12>

The reaction of M=Ru or Os) with arachno-(1-) yields the nido-metalllacarbaboranes <9,9,9-(CO)(PPh3)2-9,6-MCB8H10-5-(PPh3)> in reasonable yields as red and orange crystals respectively.A phosphine ligand is transferred from the metal atom to the cage in each case, and they both show a decarborane(14)-like cage structure with the 6- and 9-positions occupied by CH and M(CO)(PPh3)2 fragments respectively, as confirmed by single-crystal X-ray diffraction analysis.Compounds (1) and (2) are isostructural and isomorphous with their crystals are monoclinic, space group P21/n, with Z=4.R=0.087 for 2 670 observed =3.0> reflections for (1) and 0.050 for 3525 observed reflections for (2) respectively.A similar reaction with yields the arachno species <9,9,9-(eta-C5H5)(H)(PPh3)-9,6-RuCB8H12>, (3).In this case the cage arrangement as determined by a sigle-crystal X-ray diffraction study, is similar to that in (2-) with 6- and 9-positions substituted by CH2 and RuH(eta-C5H5)(PPh3) fragments, respectively.The crystals are monoclinic, space group P21/n, with Z=4, R=0.046 for 3 523 observed reflections.The application of the skeletal electron counting rules to this arachno structure is discussed.

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

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Cyclopentadienylruthenium complexes with sulphur ligands II. A comparative study of the reactivity of Ru(eta-RC5H4)Cl(L)2 (R=H, CH3, CH3CO; L=CO, Ph2PCH2CH2PPh2/2, P(CH2CH2CN)3) towards anionic (S-S) donor ligands

The complexes Ru(eta-RC5H4)Cl(PPh3)2 (R=H, CH3, CH3CO) readily react with the tertiary phosphines Ph2PCH2CH2PPh2 (dppe) and P(CH2CH2CN)3 (tcep) to give Ru(eta-RC5H4)Cl(dppe) and Ru(eta-RC5H4)Cl(tcep)2 (R=H, CH3, CH3CO).The dppe complex with R=CH3 reacts with (S2COR’)- ions to give Ru(eta-CH3C5H4)(S2COR’)(dppe) (R’=Me, Et) involving monodentate coordination of the dithiolate, and with (S2CNR’2)- ions to give Ru(S2CNR’2)2(dppe) (R’=Et).The tcep complexes do not react with the dithiolates under these conditions.The reaction of Ru(eta-C5H5)Cl(CO)2 with KS2COEt has also been studied.

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

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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. 92361-49-4, Name is Chloro(pentamethylcyclopentadienyl)bis(triphenylphosphine)ruthenium(II), molecular formula is C46H45ClP2Ru. In a Article£¬once mentioned of 92361-49-4, Computed Properties of C46H45ClP2Ru

Highly efficient atom transfer radical addition reactions with a Ru III complex as a catalyst precursor

The combination of the air-stable RuIII complex [Cp*RuCl2(PPh3)] with AIBN can be used to catalyze the atom transfer radical addition reactions of polychlorinated compounds and of sulfonyl chlorides to olefins with unprecedented turnover numbers of up to 44000. Copyright

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

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Cyclopentadienyl-Ruthenium and -Osmium Chemistry. XXII. Synthesis, X-Ray Structure and Some Reactions of RuCl(PPh3)(eta1-Ph2PCH2PPh2)(eta-C5H5), Containing a Monodentate CH2(PPh2)2 Ligand

Stoichiometric amounts of RuCl(PPh3)2(eta-C5H5) and dppm react in refluxing C6H6 to give RuCl(PPh3)(eta1-dppm)(eta-C5H5), which has been fully characterized by an X-ray study (triclinic, space group P<*>, a 22.377(6), b 9.913(2), c 9.826(3) Angstroem, alpha 70.46(2), beta 78.72(2), gamma 80.40(2) deg, Z 2) in which 3299 data were refined to R 0.046, R’ 0.052.Structural parameters are similar to those of other RuX(PR3)2(eta-C5H5) complexes.The chloro complex was converted was converted into + salts; the other PPh3 ligand can be replaced by a second dppm ligand to give +, which contains both mono- and bidentate dppm ligands.Alkylation of the uncoordinated phosphorus with Mel is accompanied by halogen exchange to give I, while reactions with a variety of transition metal complexes result in abstraction of PPh3 and formation of RuCl(dppm)(eta-C5H5).

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

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Coupling H2 to Electron Transfer with a 17-Electron Heterobimetallic Hydride: A “Redox Switch” Model for the H2-Activating Center of Hydrogenase

A meta-stable heterobimetallic mixed-valence ion, , is formed by the one-electron oxidation of Cp*(dppf)RuH <1, dppf = 1,1'-bis(diphenylphosphino)ferrocene, Cp* = pentamethylcyclopentadienide>.A remarkable stability toward one-electron oxidation is revealed by the cyclic voltammetry of 1 which contains two reversible oxidations at +0.073 and +0.541 V and a quasireversible oxidation at +0.975 V (vs NHE assigned to Ru(III/II), Ru(IV/III), and Fe(III/II), respectively.The isolable Ru(III) metal hydride, PF6 (1+), is characterized by a NIR absorption at 912 nm (epsilon = 486 M-1A cm-1) assigned to an intervalence transfer band and a series of atom transfer reactions yielding the even electron derivatives PF6 (X = H, Cl, Br, I).A crystallographically determined Fe-Ru distance of 4.383(1) Angstroem in 1 is consonant with the classification of 1+ as a weakly coupled.Type II mixed-valence ion (Hab = 627 cm-1, alpha2 = 3.3×10-3).This is the first reported example of a mixed-valence bimetallic complex containing the widely used dppf ligand.The ability of 1 to serve as a heterobimetallic catalyst for the reduction of methyl viologen with H2 makes it a unique functional model of hydrogenase enzymes.

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

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A general bifunctional catalyst for the anti-Markovnikov hydration of terminal alkynes to aldehydes gives enzyme-like rate and selectivity enhancements

A new, bifunctional catalyst for anti-Markovnikov hydration of terminal alkynes to aldehydes (6) allows practical room-temperature hydration of alkyl-substituted alkynes. Other outstanding features include near-quantitative aldehyde yields from both alkyl- and aryl-substituted alkynes and wide functional group tolerance. The uncatalyzed rate of alkyne hydration is measured for the first time, showing the enzyme-like rate and selectivity enhancements of aldehyde formation by 6. For aldehyde formation, an uncatalyzed rate <1 ¡Á 10-10 mol h-1 means a half-life >600 000, years. The catalyzed rate is up to 23.8 mol (mol 6)-1 h-1 and 10 000:1 ratio in favor of aldehyde. Changes in rate and selectivity induced by 6 are thus >2.4 ¡Á 1011 and 300 000, respectively. Copyright

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

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Ruthenium-catalyzed oxidative transformations of terminal alkynes to ketenes by using tethered sulfoxides: Access to beta-lactams and cyclobutanones

The oxidation of in situ generated Ru vinylidenes to ketenes is realized with tethered sulfoxides. The result is a Ru-catalyzed oxidative transformation of terminal alkynes to highly valuable ketenes. Moreover, the ketenes generated here were shown to undergo characteristic ketene [2+2] cycloaddition reactions with tethered alkenes and external imines, yielding synthetically versatile bicyclic cyclobutanones and beta-lactams, respectively. Oxidant included: The oxidation of in situ generated Ru vinylidenes with the help of tethered sulfoxides results in the net transformation of terminal alkynes to valuable ketenes. They undergo characteristic ketene [2+2] cycloaddition reactions with tethered alkenes and external imines, yielding synthetically versatile bicyclic cyclobutanones and beta-lactams.

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

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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, Formula: C41H35ClP2Ru

Ruthenium metallodendrimers based on nitrile-functionalized poly(alkylidene imine)s

The preparation of the first- and second-generation of nitrile- functionalized poly(alkylidene imine) dendrimers with the organometallic ruthenium complex [Ru(eta5-C5H5) (PPh 3)2Cl] peripherally attached is described. The reaction of N,N?-bis-(cyanomethyl)piperazine (1), N,N?-bis[N?,N?- bis(cyanoethyl)aminoethyl]piperazine (2), or N,N,N?,N?- tetrakis(cyanoethyl)ethylenediamine (3) with [Ru(eta5-C 5H5)(PPh3)2Cl] (4) in the presence of TlPF6 gives the new air-stable ruthenium metallodendrimers 5, 6, and 7, respectively. These stable metallodendrimers are easily prepared and represent a novel quantitative method to solidify and chromatographically purify the otherwise semi-liquid nitrile-functionalized poly(alkylidene imine) dendrimers. The compounds were fully characterized by IR and 1H, 13C, and 31P NMR spectroscopy, and mass spectrometry. These dendrimers represent the first example of the utilization of nitrile-functionalized poly(alkylidene imine)s as cores in the preparation of metallodendrimers. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.

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

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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. 14564-35-3, Name is Dichlorodicarbonylbis(triphenylphosphine)ruthenium(II), molecular formula is C38H34Cl2O2P2Ru. In a Article£¬once mentioned of 14564-35-3, name: Dichlorodicarbonylbis(triphenylphosphine)ruthenium(II)

Substituted ketene elimination from acid chlorides induced by ruthenium(0) compounds

The compound Ru(CO)2(triphos) (triphos=MeC(CH2PPh2)3) reacts with a number of acid chlorides RR’CHCOCl to form Cl and the corresponding substituted ketenes RR’CCO.A quantitative study of the reaction of Ph2CHCOCl shows that Ph2CCO is formed in a 1:1 stoichiometry.The compound Ru(CO)3(PPh3)2 also reacts with Ph2CHCOCl forming Ph2CCO and the unstable hydride Cl, the chemistry of which is also reported.

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