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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

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, Product Details of 32993-05-8

Syntheses of transition metal methoxysiloxides

The paper describes three methods for the preparation of methoxysiloxide complexes, a rare class of complexes of relevance to room temperature vulcanization (RTV) of polysiloxanes. The salt metathesis reaction involves the use of the recently described reagent NaOSi(OMe)2Me with various metal chlorides to give Cp?2Ti[OSi(OMe)2Me](OMe), (Me,MeN2N)NiOSi(OMe)2Me, (IPr)CuOSi(OMe)2Me, and (triphos)CoOSi(OMe)2Me (Cp? = C5Me5, triphos = Me(CH2PPh2)3). Several attempted reactions gave methoxide complexes instead, a pathway that is attributed to the intermediacy of kappa2-OSi(OMe)2Me species. The diol Cp?2Zr(OH)2 reacts with excess (MeO)3SiMe to give Cp?2Zr[OSi(OMe)2Me]2. In contrast the less nucleophilic Cp?2Ti(OH)2 was unreactive. The third route to methoxysiloxide complexes involves the reaction of Cp?2M(O)(py) with (MeO)3SiMe to give Cp?2M[OSi(OMe)2Me](OMe) in nearly quantitative yield (M = Ti, Zr). The structures of Cp?2Ti[OSi(OMe)2Me](OMe), Cp?2Zr[OSi(OMe)2Me](OMe), (IPr)CuOSi(OMe)2Me, and (triphos)CoOSi(OMe)2Me were confirmed by single crystal X-ray diffraction.

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

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Dimerisation and reactivity of HCCCCFc at ruthenium centres

In contrast to the simple diynyl complexes formed in reactions between HCCCCFc and MCl(dppe)Cp; (M = Fe, Ru), an analogous reaction with RuCl(PPh 3)2Cp; in the presence of KPF6 and dbu resulted in dimerisation of the diyne at the Ru centre to afford a mixture of [Ru{eta1,eta2-C(CCFc)C(L)CHCCCHFc}(PPh 3)Cp]PF6 (L = dbu 1, PPh3 2). Similar reactions with RuCl(PR3)2L gave [Ru{eta1, eta2-C(CCFc)C(dbu)CHCCCHFc}(PR3)L]PF6 (L = Cp, R = Ph 3, m-tol 4; L = eta5-C9H7, R = Ph 5). The reaction between 3 and I2, followed by crystallization of the paramagnetic product from MeOH, afforded the dicationic [Ru{C(CCFc)C(dbu) CHC(OMe)C(OMe)CHFc}(PPh3)Cp](I3)2 6. The molecular structures of 2¡¤2CH2Cl2 and 6.S (S = 2CH2Cl2, C6H6) were determined by single-crystal XRD studies.

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

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, Safety of Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II)

Preparation of ruthenium silanethiolato complexes and their reactions with sulfur dioxide; possible models for the activation of SO2 in the homogeneously catalyzed Claus reaction

CpRu(PPh3)2SSiiPr3 (6a) was prepared by reacting [CpRu(PPh3)2(acetone)]BF4 and NaSSiiPr3. Complex 6a is substitution-labile and readily gave the mixed-ligand derivatives CpRu(PPh3)(L)SSiiPr3, where L = CO (6b), PMe3 (6c), P(OMe)3 (6d), upon treatment with the corresponding ligands. CpRu(dppe)SSiiPr3 (6e) was obtained from complex 6a and dppe via the intermediate formation of CpRu(PPh3)(eta1-dppe)SSiiPr3. Treatment of complex 6a with one equivalent of SO2 gave primarily unstable CpRu(PPh3)(SO2)SSiiPr3 (6f). However, complexes 6b-e inserted one equivalent of SO2 solely at their S-SiiPr3 function to give the unstable O-silyl thiosulfito complexes CpRu(PPh3)(L)SS(O)OSiiPr3 (L = CO (8b), PMe3 (8c), P(OMe)3 (8d)) as well as CpRu(dppe)SS(O)OSiiPr3 (8e). The S-H bonds of CpRu(PPh3)2SH (7a) and CpRu(dppe)SH (7b) added to PhNSO to give CpRu(PPh3)2SS(O)NHPh (9a) and CpRu(dppe)SS(O)NHPh (9b), respectively. The crystal structure of complex 6a was determined. Crystallographic data for 6a: triclinic, P1, a = 10.642(6) A?, b = 11.068(8) A?, c = 21.994(10) A?, alpha = 79.27(5), beta= 89.22(5), gamma = 62.32(4), V = 2246(2) A?3, Z = 2.

Balanced chemical reaction does not necessarily reveal either the individual elementary reactions by which a reaction occurs or its rate law.Safety of Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II). In my other articles, you can also check out more blogs about 32993-05-8

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

Reference 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 Article, introducing its new discovery.

Some neutral ruthenium vinylidene complexes and a novel 1,3-elimination reaction: Preparation of chiral ruthenium acetylides

Reactions of RuCl(PPh3)2Cp* with 1-alkynes in non-polar solvents afford the neutral vinylidene complexes RuCl(C=CHR)(PPh3)Cp* [R = Ph (X-ray structure), But, SiMe3, CO2Me]; a novel 1,3 elimination of HCl induced by NaOMe in the presence of a variety of ligands gives the chiral-at-metal complexes Ru(C?CR)(L)(PPh3)Cp* [L = CO, C2H4 (X-ray structure), PR3, P(OR)3, O2, S2, CS2 (for example)].

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

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. 32993-05-8, C41H35ClP2Ru. A document type is Article, introducing its new discovery., Computed Properties of C41H35ClP2Ru

Mono(eta5-cyclopentadienyl)metal(II) complexes with thienyl acetylide chromophores: Synthesis, electrochemical studies, and first hyperpolarizabilities

A series of mono(eta5-cyclopentadienyl)metal-(II) complexes with nitro-substituted thienyl acetylide ligands of general formula [M(eta5 -C5H5)(L)(C?C{C4H2S}nNO2)] (M = Fe, L = K2 -DPPE, n = 1, 2; M = Ru, L= K2 -DPPE, 2 PPh3, n = 1, 2; M = Ni, L = PPh3, n = 1, 2) has been synthesized and fully characterized by NMR, FT-IR, and UV – Vis spectroscopy. The electrochemical behavior of the complexes was explored by cyclic voltammetry. Quadratic hyperpolarizabilities (beta) of the complexes have been determined by hyper-Rayleigh scattering (HRS) measurements at 1500 nm. The effect of donor abilities of different organometallic fragments on the quadratic hyperpolarizabilities was studied and correlated with spectroscopic and electrochemical data. Density functional theory (DFT) and time-dependent DFT (TDDFT) calculations were employed to get a better understanding of the second-order nonlinear optical properties in these complexes. In this series, the complexity of the push-pull systems is revealed; even so, several trends in the second-order hyperpolarizability can still be recognized. In particular, the overall data seem to indicate that the existence of other electronic transitions in addition to the main MLCT clearly controls the effectiveness of the organometallic donor ability on the second-order NLO properties of these push-pull systems. (Figure 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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Cyanide 13C NMR hyperfine shifts in paramagnetic cyanide-bridged mixed-valence complexes

Paramagnetic (hyperfine) NMR shifts in the 13C cyanide bridge and 31P resonances in a set of mixed valence complexes [(eta5-C5R5)Ru(PPh3)L( 13CN)Ru(NH3)5]n+ (R = H; L = PPh3, CO, NO+; R = Me; L = PPh3) are sensitive to the extent of intermetallic charge-transfer, and are strongly solvent dependent. The Royal Society of Chemistry.

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

Related Products 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 Article, introducing its new discovery.

Synthetic, spectral and structural studies of ruthenium(II) compounds based on 2,6-diacetylpyridinemonoxime

Reaction of the ruthenium complexes [RuCl2(EPh3)3] (E = P, As), [(eta5-C5H5)RuCl(EPh3)2] (E = P, As), [(eta5-C5Me5)RuCl(PPh3)2] and [(eta5-C9H7)RuCl(PPh3)2] with 2,6-diacetylpyridinemonoxime (dapmoH) have been investigated. Compounds with the formulations [Ru(kappa3-dapmoH)Cl(PPh3)2]PF6 (1), [Ru(kappa3-dapmoH)Cl(PPh3)2]BF4 (2) and [Ru(kappa3-dapmoH)Cl(AsPh3)2]Cl (3) have been isolated and fully characterized by elemental analyses, IR, NMR, electronic, emission spectral and electrochemical studies. Molecular structures of the complexes [Ru (kappa3 -dapmoH) Cl (PPh3)2] PF6 ¡¤ H2 O (1) and [Ru (kappa3 -dapmoH) Cl (PPh3)2] BF4 ¡¤ 1.5 H2 O (2) have been determined by single crystal X-ray diffraction studies. A structural feature of interest for both the compounds is that the counter anions in 1 and 2 play vital role in the self-assembly of cages through intermolecular weak interactions in which water dimers or trimers are encapsulated. Compounds 1 and 2 strongly emit upon excitation at their respective MLCT transitions.

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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, name: Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II)

Combined effects of metal and ligand capable of accepting a proton or hydrogen bond catalyze anti-Markovnikov hydration of terminal alkynes

A binding pocket for water is created in 1 by the imidazolyl phosphane ligands and the Ru11 center. Compound 1 proves to be an excellent catalyst for a highly selective anti-Markovnikov hydration of terminal alkynes to give aldehydes rather than isomeric ketones under near-neutral conditions (aldehyde-to-ketone ratio up to 1000:1).

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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, HPLC of Formula: C41H35ClP2Ru

Hydride Reduction of the Cations <(eta5-C5H5)Fe<(Ph2PCH2)3CMe>>PF6, <(eta5-C5H5)Ru<(Ph2PCH2CH2)2PPh>>PF6, and <(eta5-C5H5)Ru<(Ph2PCH2)3CMe>>PF6: Regioselectivity and Mechanism

Reduction of the cation <(eta5-C5H5)Fe(tripod)>PF6 with lithium aluminium hydride gives (eta5-C5H5)FeH(tripod) via an SN1 mechanism, involving prior dissociation of a phosphine ligand leading to direct attack of hydride on the metal, in contrast with the related ruthenium cations <(eta5-C5H5)RuL3>PF6 (L3 = triphos or tripod) which give the cyclopentadiene complexes (eta4-C5H6)RuL3 via exo-hydride attack on the cyclopentadienyl ligand .

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