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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, COA of Formula: C41H35ClP2Ru

Cationic Halfsandwich-Type Sulfur Dioxide Complexes of Iron and Ruthenium

Cationic halfsandwich-type complexes of sulfur dioxide, (+) (R = H, Me, M = Fe, Ru, (PR3)2 = mono- or bidentate phosphorus ligands) and (+), are obtained by ligand exchange from labile cationic (M = Fe) or neutral (M = Ru) precursors.The new compounds are characterized by IR, 1H, 13C and 31P NMR spectroscopy.Their stability increases with increasing electron density at the metal. – Key words: Iron Complexes, Ruthenium Complexes, Sulfur Dioxide

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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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Ruthenium-catalyzed hydration of 1-alkynes to give aldehydes: Insight into anti-Markovnikov regiochemistry

The mechanism of the selective conversion of 1-alkynes to aldehydes by hydration was investigated by isolating organic and organometallic byproducts, deuterium-labeling experiments, and DFT calculations. The D-labeled acetylenic hydrogen of 1-alkyne was found exclusively in the formyl group of the resulting aldehydes. After the reaction, the presence of metal-coordinated CO was confirmed. All of the experimental results strongly suggest the involvement of a metal-acyl intermediate with the original acetylenic hydrogen also bound to the metal center as a hydride, with the next step being release of aldehyde by reductive elimination. Theoretical analyses suggest that the first step of the catalytic cycle is not oxidative addition of acetylene C-H or tautomerization of eta2-alkyne to a vinylidene complex, but rather protonation of the coordinated 1-alkyne at the substituted carbon to form a metal-vinyl intermediate. This cationic intermediate then isomerizes to Ru(IV)-hydride-vinylidene via alpha-hydride migration of the vinyl group to the metal center, followed by attack of the vinylidene alpha-carbon by OH- to give the metal-hydride-acyl intermediate.

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

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Metal-assisted preparation of the alkenyl ketone and carbonyl complexes from 1-alkyne and H2O: C-C triple bond cleavage of terminal alkyne

Reactions of Cp*RhCl2(PPh3) (1) with 1-alkyne and H2O in the presence of KPF6 generated alkenyl ketone complexes [Cp*Rh(CRCHCOCH2R)(PPh3)](PF6) (2) (R = Ph (a), C6H4-p-Me (b), C6H 4-p-COOMe (c), C6H4-p-NO2 (d)). A similar complex [Cp*Rh(CPhCHCOCH2Ph)(PMePh2)] (PF6) (2e) was obtained by use of Cp*RhCl 2(PMePh2). It was revealed by X-ray analyses of 2b, 2c and 2e that the complexes 2 consist of the five-membered ring structures bound by the carbon and oxygen atoms of the alkenyl ketone group. Similar reactions of Cp*IrCl2(PPh3) (6) or (C6Me 6)RuCl2(PPh3) (7) proceeded with a cleavage of C-C triple bond of 1-alkyne without formation of an alkenyl ketone complex, affording the corresponding carbonyl complexes, [Cp*IrCl(PPh 3)(CO)](PF6) (8) or [(C6Me6) RuCl(PPh3)(CO)](PF6) (9). The diphosphine complexes [(Cp*MCl2)2{mu-diphos}] (4: M = Rh, diphos = dppm,; 12a: M = Ir, diphos = dppm; 12b: M = Ir, diphos = dppb) gave a Cl-bridged rhodium complex [{Cp*Rh(mu-Cl)}2{mu-dppm}](PF 6)2 (5), mono-carbonyl or dicarbonyl iridium complexes,[(Cp*IrCl2){mu-dppm}{Cp*IrCl(CO)}](PF 6)(13a) or [{Cp*IrCl(CO)}2{mu-dppb}](PF 6)2 (14b), respectively.

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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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Comparative study on ortho-C-H vs ortho-C-X (X = C, Cl, S) bond activation in ortho-Caromatic-N bond fusion in substituted anilines using ruthenium(II) mediators: Isolation and characterization of unusual Ru 2 complexes

The chemical reactions of a selection of ortho-mono- and disubstituted anilines with two ruthenium polyene mediator complexes, CpRu IICl(PPh3)2 (Cp- = cyclopentadienyl anion) and (Bnz)2RuII2Cl4 (Bnz = benzene), have been undertaken with a primary aim to make a comparison between ortho-C-H and ortho-C-X (X = Cl, C, S) bond activation processes in ortho-C-N bond fusion reactions. The reaction of ortho-monosubstituted anilines, viz., 2-chloroaniline (HL1a), 2-methylaniline (HL1c), and 2-methylthioaniline (HL1b), with CpRuIICl(PPh 3)2 yielded mononuclear complexes [CpRuIIL 2a-cCl] (1, 3, and 5), containing in situ generated ligands N-(aryl)-ortho-quinonediimine, L2a-c, along with anilido-bridged RuIII2 complexes (2, [CpClRuIII{mu- eta2-(L1a)-}]2; 4, [CpClRu III{mu-eta2-(L1c)-}] 2; and [6]Cl2, [CpRuIII{mu-eta2: eta1-(L1b)-}]2), respectively. The new ligands, L2a-c are formed via ortho-C-H bond activation reactions, whereas ortho-C-X bonds remained unaffected. However, the ortho-C-Cl bond activation reaction is also noted in the reaction between CpRu IICl(PPh3)2 and ortho-disubstituted aniline 2,6-dichloroaniline (HL3a) in more forceful conditions. The ruthenium(III) binuclear complex [CpRuIII{mu-eta2: eta1-(L3a)-}(mu-eta2: eta1-L2d)(mu-eta2-acetate)Ru IIICl]Cl, [7]Cl, of an in situ generated N-(2,6-dichlorophenyl)-6- chloro-ortho-quinonediimine ligand, L2d, has been isolated from the above reaction. The ligand L2d coordinates in a eta2- binding mode through an imine (=NH) nitrogen atom. The coordination mode of 2,6-dichloroanilide, (L3a)-, in [7]Cl is unusual in that an aromatic-C-Cl group is coordinated to a Ru(III) center, and it represents the first authentic crystallographic evidence of such a coordination mode in a transition metal complex. Similar reactions on a redox-inert mediator complex, (Bnz)2RuII2Cl4 (Bnz = benzene), with the aforesaid aromatic amines failed to result in ortho-C-N bond fusion reactions and afforded the mononuclear anilino complexes and an anilido-bridged RuII2 compound, [9]Cl2. The complexes have been characterized by using a host of physical methods as well as single-crystal X-ray structure determination. Their redox and spectroscopic properties have been thoroughly characterized by cyclic voltammetry and UV-vis and electron paramagnetic resonance spectroscopy. Density-functional theory calculations were employed to confirm their structural features and to support the spectral and redox properties.

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

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Some reactions of an eta3-tetracyanobutadienyl-ruthenium complex

In the eta3-butadienyl complex Ru{eta3-C(CN) 2CPhCC(CN)2}(PPh3)Cp 1, which is formed from Ru(CCPh)(PPh3)2Cp and tcne, a CN group reacts with MeO- to give the methoxy-amide Ru{NHC(OMe)C(CN)CCPhC(CN) 2}(PPh3)Cp 2, in which the NH has displaced the CC from the Ru centre with formation of a RuC3N ring. “Click addition” of azide to a CN group in 1 gives the oligomeric tetrazolato complex Ru{N3N[Na(OEt2)]CC(CN)CCPhC(CN) 2}(PPh3)Cp 3, also containing a RuC3N ring. Salt-elimination reactions of 3 with MeOTf, FeCl(dppe)Cp, RuCl(dppe)Cp* and trans-PtCl2{P(tol)3}2 result in selective substitution at one nitrogen atom of the RuC3N ring. Geometries of 1 and the anion in 3 were computed by DFT methods. Preferences for CN groups attacked in the nucleophilic and cycloaddition reactions of 1 are supported by NBO calculations. Alkylation of 1 in reactions with 1,2-dimethoxyethane gave two isomers of Ru{N3[CH(CH2OMe)(OMe)]NCC(CN)CCPhC(CN) 2}(PPh3)Cp 8 and 9, differing in the sites of attachment of the alkyl group, likely by radical processes. The molecular structures of eight complexes are reported, including a re-determination of 1. Computed NMR chemical shifts are used to reassign the butadienyl carbon resonances in the 13C NMR spectrum of 1.

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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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Novel ruthenium(II) cyclopentadienyl thiosemicarbazone compounds with antiproliferative activity on pathogenic trypanosomatid parasites

Searching for new prospective antitrypanosomal agents, three novel Ru(II)-cyclopentadienyl compounds, [Ru(eta5-C5H5)(PPh3)L], with HL = bioactive 5-nitrofuryl containing thiosemicarbazones were synthesized and characterized in the solid state and in solution. The compounds were evaluated in vitro on the blood circulating trypomastigote form of Trypanosoma cruzi (Dm28c strain), the infective form of Trypanosoma brucei brucei (strain 427) and on J774 murine macrophages and human-derived EA.hy926 endothelial cells. The compounds were active against both parasites with IC50 values in the micromolar or submicromolar range. Interestingly, they are much more active on T. cruzi than previously developed Ru(II) classical and organometallic compounds with the same bioactive ligands. The new compounds showed moderate to very good selectivity towards the parasites in respect to mammalian cells. The global results point at [RuCp(PPh3)L2] (L2 = N-methyl derivative of 5-nitrofuryl containing thiosemicarbazone and Cp = cyclopentadienyl) as the most promising compound for further developments (IC50 T. cruzi = 0.41 muM; IC50 T. brucei brucei = 3.5 muM). Moreover, this compound shows excellent selectivity towards T. cruzi (SI > 49) and good selectivity towards T. brucei brucei (SI > 6). In order to get insight into the mechanism of antiparasitic action, the intracellular free radical production capacity of the new compounds was assessed by ESR. DMPO (5,5-dimethyl-1-pirroline-N-oxide) spin adducts related to the bioreduction of the complexes and to redox cycling processes were characterized. In addition, DNA competitive binding studies with ethidium bromide by fluorescence measurements showed that the compounds interact with this biomolecule.

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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 and structural study of platinum group metal complexes containing pyrimidine bridged pyrazolyl-pyridine ligand and eta 5 and eta 6 – Cyclic hydrocarbons

The mononuclear compounds [(eta6-arene)Ru(bppm)Cl]PF 6{bppm = 4,6-bis{3-(2-pyridyl)-1H-pyrazol-1-yl}pyrimidine; arene = C6 H 6, [1]; p- i PrC6 H 4Me, [2]; C6Me6, [3]}, [CpRu(bppm)(PPh 3)]PF6{Cp = eta5-C5 H 5, [4]; eta5-C5Me5, [5]; eta5-C9 H 7, [6]} and [Cp*M(bppm)Cl] PF6 {M = Rh [7]; Ir [8]} have been synthesized from the reaction of 4,6-bis{3-(2-pyridyl)-1H-pyrazol-1-yl}pyrimidine (bppm) and the corresponding precursor metal complexes [(eta6-arene)Ru(mu-Cl)Cl]2, [CpRu(PPh3)2Cl] and [Cp*M(mu-Cl)Cl]2, respectively, in the presence of NH4 PF 6. They were characterized by the following techniques viz. IR, NMR, mass spectrometry and UV-visible spectroscopy. The molecular structures of [2] and [7] have been established by single crystal X-ray structure analyses.

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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 of NHC complexes by template controlled cyclization of beta-functionalized isocyanides

Starting from complexes of type [Ru(Cp)Cl(P-P)] (P-P = 2PPh3, 3a; P-P = 2PMe3, 3b: P-P = dppe, 3c; P-P = dppp, 3d) isocyanide complexes [Ru(Cp)(P-P)(CNR) 4a-4d (CNR = CN-CH2-CH2N 3, 1) and 7a-7d (CN-C6H4-2N3, 2) have been prepared. Reduction of the azido functions of the coordinated isocyanide ligands with Zn/NH4Cl/H2O in methanol leads to coordinated 2-amino functionalized isocyanides which cyclize to yield the complexes with a saturated NH,NH-stabilized NHC ligand 5a-5d or a benzannulated NH,NH-stabilized NHC ligand 8a-8d. The Zn/NH4Cl/H2O reduction method is of general applicability and allowed the generation of complex 11 bearing three saturated NH,NH-stabilized NHC 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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Reactivity studies of cyclopentadienyl bis(triphenylphosphine)ruthenium(II) complex towards some polypyridyl ligands

The reaction of [CpRu(PPh3)2Cl] (1) (Cp=eta5-C5H5) with excess of some potentially bridging ligands viz. 2,3-bis(alpha-pyridyl)pyrazine (bpp), 2,3-bis(alpha-pyridyl)quinoxaline (bpq), 1,3,5-tris(pyridyl)-2,4,6-triazine (tptz) and 2,3,5,6-tetrakis(pyridyl)pyrazine (tppz) yielded cationic mononuclear complexes of the type [CpRu(PPh3)(bpp)]+ (2), [CpRu(PPh3)(bpq)]+ (3), [CpRu(PPh3)(tptz)] + (4) and [CpRu(PPh3)(tppz)]+ (5), respectively. These complexes have been isolated as hexafluorophosphate salts. They were characterized by FT-IR, 1H NMR and 31P { 1H} NMR spectroscopy. The molecular structures of representative complexes 3 and 5 have been solved by single crystal X-ray crystallography.

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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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New ruthenium(II) complexes bearing N-heterocyclic carbenes

N-heterocyclic carbene complexes of ruthenium(II), [CpRu(L*)2Cl] (2) and [CpRu(CO)(L*)-Cl] (3) (Cp = eta5-C5H5; L* = l,3-dicyclohexyl-imidazolin-2-ylidene), have been obtained in high yields by reaction of [CpRu(PR2R?)2Cl] (R = R? = Ph, la; R = Ph, R? = 2-MeC6H4, 1b) and [CpRu(CO){PPh2(2-MeC6H4)}Cl] (1c), respectively, with the free carbene L*. The mixed dicarbene complex [CpRu(=CPh2)(L*)Cl] (4) is prepared from [CpRu(=CPh2){PPh2(2-MeC6H4-Cl] (1d) and an equimolar amount of L*, whereas subsequent reaction of 1d with L* leads to formation of 2, along with tetraphenylethene. The reaction of [Cp*Ru(PPh3)2Cl] (1e) with L* gives the pentamethylcyclopentadienyl derivative [Cp*Ru(PPh3)(L*)Cl] (5) (Cp* = eta5-C5Me5) by displacement of 1 equiv of PPh3 Complex 5 reacts in toluene with CO, pyridine (Py), and N2CHCO2Et, affording [Cp*Ru(CO)(L*)Cl] (6), [Cp*Ru(Py)(L*)Cl] (7), and the mixed dicarbene [Cp*Ru(=CHCO2Et)(L*)Cl] (8), which were isolated in high yields. The molecular structure of complex 6 has been determined by an X-ray investigation, and the carbene-ruthenium distance clearly indicates a single bond (2.0951(18) A). The N-heterocyclic carbene does not undergo substitution by other two-electron ligands.

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