Discovery of Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II)

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Hexasubstitution of apical triflate ligands in the octahedral clusters [M]2[Mo6X8(CF3SO3) 6] (M = n-Bu4N or Cs, X = Br or I) and monosubstitution in [n-Bu4N]2[Mo6Br13(CF 3SO3)] was carried out in tetrahydrofuran at 60C with simple pyridines and then extended to organometallic pyridines, yielding cluster-cored stars, and to dendronic polyallyl-and polyferrocenylpyridines, yielding cluster-cored polyallyl and polyferrocenyl dendrimers and dendrons. The orange pyridine-substituted clusters, whose pyridine protons are deshielded in 1H NMR (a practical tool for characterization), are air-stable and thermally stable with simple pyridines, light- and air-sensitive with organometallic pyridines, and air-fragile and thermally fragile with large dendronized pyridines.

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

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

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Ruthenium piano-stool complexes incorporating the new bidentate aminoalkylphosphine ligand 1,2-bis(dipyrrolidin-1-ylphosphino)ethane (dpyrpe, I) or its monodentate counterpart bis(pyrrolidin-1-yl)methylphosphine (pyr 2PMe, II) have been prepared, [(C5R5)RuCl(PP)] (R = Me and PP = dpyrpe, 1; R = Me and PP = (pyr2PMe)2, 2; R = H and PP = dpyrpe, 3). Complexes 2 and 3 have been characterized by X-ray crystallography. Complexes 1 and 2 react with NaBAr4f in the presence of ligand L to yield [Cp*Ru(L)(dpyrpe-kappa2P)] [BArf4] (L = MeCN, 4a; CO, 4b; N2, 4c) and [Cp*Ru(L)(pyr2PMe)2][BAr4f] (L = MeCN, 5a; CO, 5b; N2, 5c). Complex 4a was crystallographically characterized. The CO complexes 4b and 5b were examined using IR spectroscopy in an attempt to establish the electron-donating capabilities of I and II. Complex 1 oxidatively adds H2 in the presence of NaBAr4 f to yield the Ru(IV) dihydride [Cp*RuH2(dpyrpe- kappa2P)][BAr4f], 7.

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

Discovery of Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II)

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Anticancer activity of the new [Ru(eta5-C5H 5)(PPh3)(Me2bpy)][CF3SO 3] (Me2bpy = 4,4?-dimethyl-2,2?-bipyridine) complex was evaluated in vitro against several human cancer cell lines, namely A2780, A2780CisR, HT29, MCF7, MDAMB231 and PC3. Remarkably, the IC50 values, placed in the nanomolar and sub-micromolar range, largely exceeded the activity of cisplatin. Binding to human serum albumin, either HSA (human serum albumin) or HSAfaf (fatty acid-free human serum albumin) does not affect the complex activity. Fluorescence studies revealed that the present ruthenium complex strongly quench the intrinsic fluorescence of albumin. Cell death by the [Ru(eta5-C5H5)(PPh 3)(Me2bpy)][CF3SO3] complex was reduced in the presence of endocytosis modulators and at low temperature, suggesting an energy-dependent mechanism consistent with endocytosis. On the whole, the biological activity evaluated herein suggests that the complex could be a promising anticancer agent.

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

Extracurricular laboratory:new discovery of Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II)

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Herein are described some continuing investigations into the reactions of cyano-alkenes with diynyl-ruthenium complexes which have resulted in the preparation and characterisation of diynyl-ruthenium compounds Ru(C?CC?CR)(PP)Cp [R = Ph, PP = dppe; R = Fc, PP = dppf; R = CPh=CBr2, PP = (PPh3)2], together with the polycyanobutadienyls Ru{C?CC[=C(CN)2]CR=CR?(CN)}(PP) Cp? [R = Fc, (PP)Cp? = (dppf)Cp; R = H, SiMe3, (PP)Cp? = (dppe)Cp*] formed by [2 + 2]-cycloaddition of the cyano-alkenes to the outer C?C triple bonds and subsequent ring-opening reactions. Single-crystal XRD molecular structure determinations of six complexes are reported. Copyright

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

Final Thoughts on Chemistry for Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II)

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We have designed and synthesized oligosubstituted bullvalenes 1 and 2 as adaptive molecules that can change their shapes in order to bind tightly to a suitable guest. By incorporation of a photolabile o-nitroveratryloxycarbonate (NVOC) group into bullvalenes 1 and 2, tightly binding species can be selectively isolated from a population of hundreds of interconverting structural isomers. Spontaneous strain-assisted Cope rearrangements allow these shape-shifting molecules to exist in a dynamic equilibrium of configurationally distinct valence isomers, as revealed by dynamic NMR and HPLC studies. When NVOC bullvalenes 1 and 2 were exposed to UV light, the cleavage of the NVOC group resulted in a mixture of static isomers of the corresponding bullvalone. Binding studies of NVOC bisporphyrin bullvalene 1 demonstrated that the dynamic isomeric equilibrium shifted in the presence of C60, favoring configurations with more favorable binding affinities. Irradiation of a mixture of 1 and C60 with UV light and isolation of the major static isomer yielded an isomer of bisporphyrin bullvalone with a binding affinity for C 60 that was ?2 times larger than that of the nonadapted isomer bisporphyrin bullvalone 41.

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

Awesome and Easy Science Experiments about Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II)

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[Figure Presented] The wizard of Os: Regioselective osmiumcatalyzed 7-endo heterocyclization of aromatic alkynols affords benzoxepines in good yields. The proposed catalytic cycle involves the key formation of osmiumvinylidene complexes via an alkynyl-hydride-osmium(IV) complex from the starting alkynol.

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

Awesome and Easy Science Experiments about Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II)

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The 1-alkyne-1-thiolates R-CC-Sli <1: R = SiMe3, 3: (eta5-C5H4)Fe(eta5-C5H5)> react with (Ph3P)2PtCl2 and CpRu(PPh3)2Cl to give the complexes trans-(Ph3P)2Pt(S-CC-SiMe3)2 (4a).CpRu(PPh3)2S-CC-SiMe3) (4b), and cis-(Ph3P)2Pt(S-CC-eta5-C5H4)Fe(eta5-C5H5)>2 (5).The Pt(II)bis(acetylide) complex cis-(Ph3P)2Pt2 (6a) was isolated after chromatography of 5.The trans-configurated compound 6b is obtained by the reaction of Fe(eta5-C5H5) with (Ph3P)2PtCl2.The complexes are characterized by IR, 1H-, 13C-, and 31P-NMR spectroscopy, FAB mass spectrometry and X-ray diffraction (6a). – Key Words: 1-Alkyne-1-thiolato ligands / Bis(acetylide) complexes / Ferrocene derivatives / Ruthenium complexes / Platinum complexes

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

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The eta3-allylic complex 8 was obtained from thermolysis of the neutral ruthenium furyl complex 7 with an unsaturated carbon chain on the furyl ligand. Protonation of complex 8c with HBF4 generates complex 9c with an oxygen atom andan olefin group coordinated to the ruthenium metal.

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

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New ruthenium(II) and iron(II) organometallic compounds of general formula [(eta5-C5H5)M(PP)Lc][PF6], bearing carbohydrate derivative ligands (Lc), were prepared and fully characterized and the crystal structures of five of those compounds were determined by X-ray diffraction studies. Cell viability of colon cancer HCT116 cell line was determined for a total of 23 organometallic compounds and SAR’s data analysis within this library showed an interesting dependency of the cytotoxic activity on the carbohydrate moiety, linker, phosphane coligands, and metal center. More importantly, two compounds, 14Ru and 18Ru, matched oxaliplatin IC50 (0.45 muM), the standard metallodrug used in CC chemotherapeutics, and our leading compound 14Ru was shown to be significantly more cytotoxic than oxaliplatin to HCT116 cells, triggering higher levels of caspase-3 and -7 activity and apoptosis in a dose-dependent manner.

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