Discovery of Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II)

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The complex [RuCp(PPh3)2(HdmoPTA)](OSO2CF3)2 (2; HdmoPTA = 3,7-H-3,7-dimethyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane) was synthesized and characterized. Its crystal structure was determined by single-crystal X-ray diffraction. The complex showed a more potent antiproliferative activity than cisplatin against a representative panel of human cancer cells.

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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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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, Recommanded Product: 32993-05-8

Hydrative dimerization and hydration of allenes proceeded in the presence of a ruthenium catalyst and a strong acid such as trifluoroacetic acid. gamma,delta-Unsaturated ketones and methyl ketones were isolated in moderate combined yields. No isomeric compound (isomeric enone) was isolated. Copyright

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

Awesome Chemistry Experiments For Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II)

Sometimes chemists are able to propose two or more mechanisms that are consistent with the available data.Formula: C41H35ClP2Ru, If a proposed mechanism predicts the wrong experimental rate law, however, the mechanism must be incorrect.Welcome to check out more blogs about 32993-05-8, in my other articles.

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The P-Ph cleavage of phenyldibenzophosphole (1) with lithium in THF gives lithium dibenzophospholide (2). Reaction of 2 with ethyleneglycol ditosylate produces the known chelate ligand 1,2-bis(dibenzophospholyl)ethane (3) in good yield. Similarly, 2 and (2R,3R)-butanediol ditosylate give the new chiral chelate ligand (2S,3S)-bis(dibenzophospholyl)butane (4). Ligand exchange of [CpRu(PPh3)2Cl] with 3 or 4 yields the halfsandwich complexes [CpRu(C12H8PC2H4PC12H8)Cl] (5) and [CpRu((S,S)-C12H8PCHMeCHMePC12H8)Cl] (6). Complex 6 was characterized crystallographically (monoclinic, space group P21 (no. 4), a=820.6(4), b=1501.0(3), c=1172.8(6) pm, beta=108.87(2), V=1.367(1)×109 pm3, Z=2). The most conspicuous feature of the structure of 6 is the perfect coplanarity of the two dibenzophosphole moieties imposed by their steric interaction with the Cp ligand. Complex 6 and the thiophene complex [CpRu((S,S)-C12H8PCHMeCHMePC12H8)(SC 4H4)]BF4 (7) derived therefrom are remarkably unreactive with regard to ligand substitutions. A possible explanation is the lack of intramolecular M…H-C stabilization en route to the transition state of ligand substitution. The enantiomeric purity of 6 and 7 could nevertheless be demonstrated by conversion to diastereomerically pure [CpRu((S,S)-C12H8PCHMeCHMePC12H8)((S )-CNCHMePh)]BF4 (8).

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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 kinetics of phosphine substitution in CpRu(PPh3)2X (X = Br, 1b, X = I, 1c, X = N3, 1d, and X = NCO, 1e) have been measured under pseudo-first order conditions in THF solution and compared with data for CpRu(PPh3)2X (1a). The relative rate of substitution is found to be 1a > 1d > 1b > 1e > 1c. Substitution rates decrease in the presence of added PPh3 and are independent of added X consistent with a dissociative process. Activation parameters for 1a-1c (DeltaH? = 113-135 kJ mol-1, DeltaS? = 21-102 J mol-1 K-1) and DFT calculations support a dissociative or dissociative interchange pathway even though negative activation entropies (DeltaS? = -48 ± 16 to -105 ± 5 J mol-1 K-1) are observed for 1d-e. Differences in Ru-ligand bond angles in 1d-e point to different pi-acceptor properties of the pseudohalide ligands, contributing to the faster rate of substitution for the azide complexes, 1d relative to the cyanate derivative 1e. Substitution is not observed when X = F, 1f, X = H, 1g, X = SnF3, 1h, or X = SnCl3, 1i. Compounds 1b-1e also react with chloroform to yield 1a. The rates of halide exchange are comparable to phosphine substitution for 1c and 1d. The latter reaction is inhibited by excess triphenylphosphine and is unaffected by both radical inhibitors and radical traps suggesting that a radical mechanism is unlikely.

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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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A series of ruthenium and osmium complexes containing highly fluorous diphosphine ligands FP?PF = (F 13C6C6H4p)2P(CH 2)2P(p-C6H4C6F 13)2 (dfppe) and (F13C6C 6H4-p)2P(CH2)3P(p-C 6H4C6F13)2 (dfppp) has been prepared. The fluorous diphosphine ligands incorporate four C 6F13 “fluoro-ponytails”, and these have been effective in solubilizing the complexes in supercritical carbon dioxide (scCO2). Precise solubility measurements in scCO2 were performed for some of the complexes. The new complexes [MX2( FP?PF)2] and [MX( FP?PF)(eta-C5H5)], M = Ru, Os, X = Cl, Br, have been characterized by a number of spectroscopic techniques and their electrochemical properties measured, three of the ruthenium complexes also being characterized by single-crystal X-ray studies. The noncovalent interactions observed in the X-ray structures have been analyzed by the Hirshfeld surface approach, putting them on a more solid footing. The fluorinated complexes show significantly different solvation properties from those of the analogous unfluorinated compounds, particularly with respect to their behavior in common organic solvents and their good scCO2 solubility.

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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 bis-bidentate ligand, 1,3-bis((3-(pyridin-2-yl)-1H-pyrazol-1-yl)methyl)benzene (NN?NN), containing two chelating pyrazolyl-pyridine units connected by an aromatic spacer with platinum group metal complexes results in a series of cationic binuclear complexes, [(eta6-arene)2Ru2(NN?NN)Cl2]2+ (arene = C6H6, 1; p-iPrC6H4Me, 2; C6Me6, 3), [(eta5-C5Me5)2M2(NN?NN)Cl2]2+ (M = Rh, 4; Ir, 5), [(eta5-C5H5)2M2(NN?NN)(PPh3)2]2+ (M = Ru, 6; Os, 7), [(eta5-C5Me5)2Ru2(NN?NN)(PPh3)2]2+ (8) and [(eta5-C9H7)2Ru2(NN?NN)(PPh3)2]2+ (9). All these complexes have been isolated as their hexafluorophosphate salts and fully characterized by use of a combination of NMR spectroscopy, IR spectroscopy and mass spectrometry. The solid state structures of three complexes, [2][PF6]2, [4][PF6]2 and [6][PF6]2, has been determined by X-ray crystallographic studies.

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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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A new method to convert terminal alkynes under relatively mild conditions to 1-cyanoalkynes using in situ formed cyanogen is described. 1-Cyanoalkynes have a higher reactivity than terminal alkynes in the ruthenium(II)-catalyzed regiospecific azide-alkyne cycloaddition to afford 4-cyano-1,2,3-triazoles. A mechanistic proposal different from the one that terminal alkynes adopt under the same reaction conditions is proposed. This work provides a new and convenient two-step sequence to prepare 4-cyano-1,2,3-triazoles from terminal alkynes and organic azides.

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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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Thermolysis of [CpRuCl(PPh3)2] and NaS 2CNPr2 or NaS2CNMeBu in methanol affords the ruthenium(II) dithiocarbamate complexes, [CpRu(PPh3)(S 2CNPr2)] and [CpRu(PPh3)(S2CNMeBu)], which have been crystallographically characterized. A similar treatment of two equivalents of [CpRuCl(PPh3)2] with the bis(dithiocarbamate) ligand derived from 1,3-homopiperazine affords [{CpRu(PPh3)}2(mu-S2CNC5H 10NCS2)].

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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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Reaction of the readily available metal acetylide complexes Ru(CCC 6H4R-4)(PPh3)2Cp (R = OMe, Me, H, CN, CO2Me), Ru(CCFc)(PPh3)2Cp and Fe(CCC 6H4R-4)(dppe)Cp (R = Me, H) with 1-cyano-4- dimethylaminopyridinium tetrafluoroborate affords cyanovinylidene complexes [Ru{CC(CN)C6H4R-4}(PPh3)2Cp]BF 4, [Ru{CC(CN)Fc}(PPh3)2Cp]BF4 and [Fe{CC(CN)C6H4R-4}(dppe)Cp]BF4 in an experimentally simple fashion. These synthetic studies are augmented by refinements to the preparation of the key iron reagents FeCl(dppe)Cp and Fe(CCC6H4R-4)(dppe)Cp. Molecular structure determinations, electrochemical measurements, representative IR spectroelectrochemical studies and DFT studies have been used to provide insight into the electronic structure of the cyanovinylidene ligand, and demonstrate that despite the presence of the cyano-substituted methylidene fragment, reduction takes place on the vinylidene Calpha carbon.

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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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Several new compounds of the type (1+) X(1-), where X = Cl, Br, I, I3, BPh4, p-toluenesulphonate, d(+)-campho-10-sulphonate, have been obtained in the form of ion pairs or salts.The above compounds form during oxidative addition by HX acids to CpOsH(PPh3)2.The reactions are complete after several seconds, with a quantitative yield.This is in contrast to the behaviour of CpRuH(PPh3)2, where covalent CpRuX(PPh3)2 forms.Reaction of CpOsH(PPh3)2 with DCl acid (excess) gives Cl, but no Cl is formed.Refluxing CpOsBr(PPh3)2, in ethylene glycol for instance, gives a (1+) cation as a result of the dehydrogenation of the glycol.Compounds of the type, X, in solutions of polar solvents (MeOH) or halogenated hydrocarbons (e.g.CH2X2) undergo transformation to CpOsX(PPh3)2 during the reductive elimination process.In this way novel CpOsI(PPh3)2 has been obtained.In the case of the reaction of a mixture of HX + X2 with CpOsH(PPh3)2, Br3 (for Br2) and I3 (for I2) have been obtained in the form of sparingly soluble ion pars with yields of about 90percent.

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