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Helices of ruthenium complexes involving pyridyl-azine ligands: Synthesis, spectral and structural aspects

New cationic complexes [Ru(eta5-C5H5 (EPh3)(L)]BF4 [L = pyridine-2-carbaldehyde azine (paa); E = P, 1; E = As, 2; E = Sb, 3] and kappa1 bonded dppm complexes [Ru(eta5-C5H5 (kappa1-dppm)(L)]BF4 [L = paa 4; L = p-phenylene-bis(picoline)aldimine (pbp) 5] containing both group V donor and pyridyl-azine ligand are reported. The complexes were fully characterized by analytical and spectral studies. 31P NMR spectral studies suggested coordination of dppm in the complexes 4 and 5 in kappa1-manner, which was further, confirmed by structural studies on the representative complex 4. Weak interaction studies revealed that inter- and intramolecular C-H?X (X = O, F, Cl, pi) and pi-pi interactions in the complexes 1 and 4 lead to helical structures.

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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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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, Application In Synthesis of Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II)

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

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Synthesis, characterization and cytotoxicity of cyclopentadienyl ruthenium(II) complexes containing carbohydrate-derived ligands Dedicated to Prof. Maria Jose Calhorda on the occasion of her 65th birthday.

We here report the synthesis of new cyclopentadienyl ruthenium(II) complexes of general formula [(eta5-C5H 5)Ru(PP)(L)]+ (PP = two triphenylphosphine, 1,2-diphenylphosphinoethane), isolated as PF6- salts, with L being galactose and fructose carbohydrate derivative ligands, N-coordinated to the metal centre by nitrile, tetrazole and 1,3,4-oxadiazole moieties. The ten new organometallic compounds were fully characterized by FT-IR, 1H, 13C, and 31P NMR spectroscopies, and by elemental analysis. The cytotoxicity of the ruthenium(II) compounds was tested on HeLa cancer cells (cervical carcinoma), unveiling IC50 values in the low micromolar range.

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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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Electron-Rich Ruthenium Thiolate Complexes, Synthesis and Reactions with Electrophiles

Ruthenium thiolates (PR’3 = PPh3, 1/2 dppe, 1/2 dppm, R = Me, CH2Ph) are obtained from the corresponding chlorides and NaSR.PPh3 is readily exchanged for CO to give the chiral complexes .Alkylation with methyl tosylate yields the cations + and +, which were isolated as their PF6- salts.The neutral carbonyls add dimethyl acetylenedicarboxylate giving five-membered metallocycles.

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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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Conjugated Vinylgold(I)-Vinylideneruthenium(II) Complexes and Related Organoruthenium Compounds: Stable Analogues of Intermediates Proposed in Dual Gold Catalysis

The reaction of a platinum acetylide derived from a 1,2-dialkynylarene with a phosphanegold(I) species delivered a sigma-platinum-pi-gold coordination to the same triple bond of the organic substrate. Cyclopentadienyl-di(phosphanyl)ruthenium(II) acetylides of the same substrate type gave vinylgold(I)-vinylideneruthenium(II) complexes in similar reactions. A switch to the corresponding cyclopentadienyl-di(carbonyl)ruthenium(II) species with a phenyl group on the second alkyne provided vinylruthenium(II) complexes in which the ruthenium was still bound to the same carbon as in the starting material, with a tert-butyl group on the second alkyne vinylruthenium(II) complexes in which the ruthenium has migrated to another carbon, were obtained. This reactivity mimics the initial steps suggested for dual gold catalysis with these substrates and thus for the first time experimentally confirms the organometallic reactivity patterns proposed for the single steps.

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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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Cyclopentadienyl-ruthenium and -osmium complexes IX. Cation formation of cyclopentadienylruthenium complex molecules by the CpRu+ cation during reflux in alcohols or glycols

Information from MS(FD) and (EI) investigations of compounds containing fragment is presented.In a few cases cation formation gives the new extended cations having m/e values above those of starting parent ions, enlarged by a 167 unit.An analogous process, taking into account the final product, can occur during reflux of the starting compounds, e.g.CpRuX(PPh3)2 type (X = Cl, Br, I) in glycols or lowboiling alcohols.In the last case the access of oxygen, playing the role of the labilizing agent of the PPh3 ligands, is necessary.The phosphorus NMR studies ofthe dinuclear cations + as well as the application of the rule on the effect of the methyl substituent at Cp-ring on changes in the phosphorus NMR spectra, are described in detail.

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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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Trifluoromethanesulfonato derivatives of ruthenium(II)

The reactivity of Ru(O2CNiPr2) 2(CO)2(PPh3)2 (1), towards CF 3SO3H (TfOH, trifloromethanesulfonic acid or triflic acid) has been studied and the products [Ru(O2CNiPr 2)(CO)2(PPh3)2][OTf] (2), and Ru(OTf)2(CO)2(PPh3)2 (3), have been obtained, the former being structurally characterised as one of the few examples of cationic N,N-dialkylcarbamato complexes. In compound 2, the N,N-di-iso-propylcarbamato group is bidentate. In experiments aimed at obtaining Ru(OTf)2(CO)2(PPh3)2 according to the literature method, i.e. from Ru(CO)3(PPh 3)2 and TfOH, the intermediate species [RuH(CO) 3(PPh3)2][OTf] (4), corresponding to the oxidative addition of triflic acid, has been intercepted. Treatment of this derivative in refluxing toluene followed by addition of methanol afforded the compound [RuH(CO)2(PPh3)2(CH 3OH)][OTf] (5), which has been characterised by single-crystal X-ray diffractometry.

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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 VERSATILE ROUTE TO (eta5-C5R5)RuL2X FROM ALLYLMETHYLRUTHENIUM COMPLEXES

Divalent ruthenium complexes, (eta5-C5R5)RuL2X (R=H, CH3; X=Br, Cl), are formed by thermal decomposition of (eta5-C5R5)Ru(CH3)X(eta3-C3H5) in the presence of several neutral ligands.

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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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Spectroscopic and electrochemical investigation of coordination complexes of octakis(benzylthio)tetraazaporphyrincobalt(II)

Synthesis of new bichromophoric di- and pentanuclear complexes 2-7 by datively binding (bpy)2RuII, (phen)2Ru II and Cp (PPh3)RuII units to the periphery of [Co(OBTTAP)], 1, and their spectroscopic properties are described. IR, 1H NMR, UV-Vis, and mass spectral data were used for their characterization. Relative intensities and positions of the Soret and Q-bands absorptions in the di- and pentanuclear complexes were observed shifted vis-a-vis that in the precursor complex [Co(OBTTAP)], 1. These complexes particularly, those possessing [Co(OBTTAP)] and (bpy)2Ru II/(phen)2RuII units, exhibited efficient inter-component electronic excitation energy transfer in their fluorescence excitation-emission spectra, that are suggestive of a high degree of inter-component electronic interaction in them. Also, the electrode activity of the complexes improved upon binding of the peripheral units and they exhibited multiple one-electron reversible oxidation waves in the cyclic voltammograms. These effects have been explained in terms of dpi(S)-dpi(Ru) interactions.

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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 straightforward access to ruthenium-coordinated fluorophosphines from phosphorous oxyacids

The transformation of phosphorous oxyacids into the corresponding fluorophosphines was mediated by [RuCp(PPh3)2Cl] under mild reaction conditions using a soft deoxofluorinating agent. The reaction is selective, proceeds with high yields and can be extended to a wide range of phosphorous oxyacids once coordinated to the ruthenium synthon [RuCp(PPh3)2]+ as their hydroxyphosphine tautomer. Deoxofluorination of phenylphosphinic acid was also mediated by [RuCpR(CH3CN)3]PF6, where CpR: Cp = C5H5, Cp? = C5Me5, and [Ru(eta6-p-cymene)(mu-Cl)Cl]2. X-Ray single crystal structures of the two new derivatives, [RuCp(PPh3)2{PhP(OH)2}]CF3SO3 and [Ru(eta6-p-cymene)Cl2{PhP(OH)2}] have been determined.

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