Archives for Chemistry Experiments of (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium

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Total synthesis of spirastrellolide F methyl ester – part 2: Macrocyclization and completion of the synthesis

(figure represented) Marvel of the sea: A concise and highly convergent total synthesis of the methyl ester of the marine macrolide spirastrellolide F (see picture), which has exquisite antimitotic properties, is reported. In this approach, the northern and the southern hemispheres of this intricate target are stitched together in only two consecutive steps (Suzuki coupling, Yamaguchi lactonization) without any interim protectinggroup manipulations.

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

Discovery of Ruthenium(III) chloride

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Electrocatalytic oxidation of preadsorbed monolayer of CO on polycrystalline Pt60-Ru40 electrocatalyst: Nucleation and growth of oxygen-containing species

The kinetics and mechanism of nucleation and growth of oxygen-containing-species, during the electro-oxidation of preadsorbed saturated monolayer of CO on polycrystalline Pt60-Ru40 electrodeposited catalysts, were investigated in a CO-free perchloric acidic solution, using stripping voltammetry and potentiostatic pulse technique. The surface composition of investigated catalysts was determined using XPS. The plots of CO oxidation rate vs. time (j-t curves) displayed responses quite typical for the processes controlled by the nucleation and growth phenomena. Therefore, the overall rate of the CO oxidation reaction can be expressed in terms of the rate of nucleation and growth of oxygen-containing species in adsorbed CO monolayer. With the increase in CO oxidation potential above +0.5 V vs. NHE, the change from a 2D-kinetically controlled nucleation to a 3D-diffusionally controlled nucleation mechanism was observed. Enhanced electrocatalytic activity of the investigated Pt-Ru surface toward CO electro-oxidation, compared to pure Pt surface, was discussed in terms of the propensity of Ru atoms nucleation sites toward the adsorption of oxygen-containing species and in respect to the observed difference in the intrinsic rate constants for CO oxidation on Pt vs. Ru surface atoms. Potentiostatic and voltammetric CO stripping experiments clearly showed the bifunctional character of our Pt-Ru catalyst, with enhanced synergistic properties.

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

Extracurricular laboratory:new discovery of Dichloro(benzene)ruthenium(II) dimer

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Synthesis and characterization of some homo/hetero binuclear hydrido carbonyl ruthenium(II) polypyridyl complexes

Mononuclear hydrido carbonyl complex [RuH(CO)(PPh3) 2-(eta2-tptz)]BF4 (tptz = 2,4,6-tris-(2?-pyridyl)-1,3,5-triazine) has been used as a building block in the synthesis of homo/hetero binuclear complexes. The complex [RuH(CO)(PPh3)2(tptz)]BF4 behaves as a potential metallo-ligand. Its reaction with different molecules ranging from K2PtCl4, [PdCl2(PhCN)2], chloro-bridged dimeric arene ruthenium complexes [{Ru(eta 6-arene)(mu-Cl)Cl}2] (arene = p-cymene or benzene), [{Rh(eta5-C5Me5)(mu-Cl)Cl}2] and [Rh(COD)(mu-Cl)]2 (COD = 1,5-cyclooctadiene) leads to the formation of binuclear complexes. The homo and hetero binuclear tptz bridged complexes [RuH(CO)(PPh3)2(mu-tptz)PtCl 2]BF4, [RuH(CO)(PPh3)2(mu -tptz)PdCl2]BF4, [RuH(CO)(PPh3) 2(mu-tptz)-(eta6-C10H 14)RuCl](BF4)2, [RuH(CO)(PPh3) 2(mu-tptz)(eta6-C6Me 6)-RuCl](BF4)2, [RuH(CO)(PPh3) 2(mu-tptz)(eta2-COD)Rh](BF4)2 and [RuH(CO)(PPh3)2(mu-tptz)Rh(eta5-C 5Me5)Cl](BF4)2 have been synthesized and characterized using IR, NMR, ESMS and FAB mass spectra.

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

Awesome and Easy Science Experiments about Ruthenium(III) chloride

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Studies on Pd(II), Pt(II), Ru(III), Rh(III), Ir(III) and Os(IV) complexes of N-methylcyclohexyldithiocarbamate

N-Methylcyclohexyldithiocarbamato complexes of the type, Mn have been synthesised and characterised on the basis of electrical conductance, magnetic susceptibility, spectral (IR, UV, visible) and thermal (TG, DTA) studies.

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

Final Thoughts on Chemistry for Dichloro(benzene)ruthenium(II) dimer

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Continuous-flow asymmetric hydrogenation of the beta-keto ester methyl propionylacetate in ionic liquid-supercritical carbon dioxide biphasic systems

A continuous-flow process for the asymmetric hydrogenation of methyl propionylacetate as a prototypical beta-keto ester in a biphasic system of ionic liquid and supercritical carbon dioxide (scCO2) is presented. An established ruthenium/2,2?-bis(diphenylphosphino)-1,1?-binaphthyl (BINAP) catalyst was immobilised in an imidazolium-based ionic liquid while scCO2 was used as mobile phase transporting reactants in and products out of the reactor. The use of acidic additives led to significantly higher reaction rates and enhanced catalyst stability albeit at slightly reduced enantioselectivity. High single pass conversions (>90%) and good enantioselectivity (80-82% ee) were achieved in the first 80h. The initial catalyst activity was retained to 91% after 100h and to 69% after 150h time-on-stream, whereas the enantioselectivity remained practically constant during the entire process. A total turnover number of ?21,000 and an averaged space-time yield (STYav) of 149g L-1 h -1 were reached in a long-term experiment. No ruthenium and phosphorus contaminants could be detected via inductively coupled plasma optical emission spectrometry (ICP-OES) in the product stream and almost quantitative retention by the analysis of the stationary phase was confirmed. A comparison between batch-wise and continuous-flow operation on the basis of these data is provided. Copyright

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

Final Thoughts on Chemistry for 246047-72-3

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Synthesis of novel quaternary amino acids using molybdenum-catalyzed asymmetric allylic alkylation

The Mo-catalyzed asymmetric allylic alkylation using azlactones provides extraordinary levels of selectivity. Thus, a wide range of cinnamyl-type substrates react with 2-methyl and 2-benzyl azlactones to give only the product resulting from attack at the more substituted carbon. Using other alkyl substituents such as 2-methylthioethyl, isobutyl, allyl, and isopropyl provides products that still retain excellent regioselectivity but small quantities of the linear product are also observed. In all cases, excellent diastereo- and enantioselectivity of the branched alkylated product are observed. This new asymmetric reaction provides ready access to unusual quarternary amino acids, important building blocks for biological applications. The reactions complements the Pd AAA wherein the cinnamyl substrate leads to only the product of attack at the primary terminus of the allyl moiety. Copyright

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

Some scientific research about (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium

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Trimethylsumanene: Enantioselective synthesis, substituent effect on bowl structure, inversion energy, and electron conductivity

C3 symmetric chiral trimethylsumanene was enantioselectively synthesized through Pd-catalyzed syn-selective cyclotrimerization of an enantiomerically pure iodonorbornenone, ring-opening/closing olefin metathesis, and oxidative aromatization where the sp3 stereogenic center was transmitted to the bowl chirality. Chiral HPLC analysis/resolution of the derivatives were also achieved. Based on theoretical calculations, the columnar crystal packing structure of sumanene and trimethylsumanene was interpreted as due to attractive electrostatic or CH-pi interaction. According to the experimental and theoretical studies, the bowl depth and inversion energy were found to increase on methylation for sumanene in contrast to corannulene. Dissimilarities of the effect of methylation on the bowl structure and inversion energy of sumanene and corannulene were ascribed to differences in steric repulsion. A double-well potential model was fitted to the bowl structureinversion energy correlation of substituted sumanenes, with a small deviation. The effects of various substituents on the sumanene structure and bowl-inversion energy were analyzed by density functional theory calculations, and it was shown that the bowl rigidity is controlled by a combination of electronic and steric effects of the substituents. The electron conductivity of trimethylsumanene was investigated by time-resolved microwave conductivity method, compared with that of sumanene.

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

Final Thoughts on Chemistry for 246047-72-3

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Asymmetric Induction and Enantiodivergence in Catalytic Radical C-H Amination via Enantiodifferentiative H-Atom Abstraction and Stereoretentive Radical Substitution

Control of enantioselectivity remains a major challenge in radical chemistry. The emergence of metalloradical catalysis (MRC) offers a conceptually new strategy for addressing this and other outstanding issues. Through the employment of D2-symmetric chiral amidoporphyrins as the supporting ligands, Co(II)-based MRC has enabled the development of new catalytic systems for asymmetric radical transformations with a unique profile of reactivity and selectivity. With the support of new-generation HuPhyrin chiral ligands whose cavity environment can be fine-tuned, the Co-centered d-radicals enable to address challenging issues that require exquisite control of fundamental radical processes. As showcased with asymmetric 1,5-C-H amination of sulfamoyl azides, the enantiocontrol of which has proven difficult, the judicious use of HuPhyrin ligand by tuning the bridge length and other remote nonchiral elements allows for controlling both the degree and sense of asymmetric induction in a systematic manner. This effort leads to successful development of new Co(II)-based catalytic systems that are highly effective for enantiodivergent radical 1,5-C-H amination, producing both enantiomers of the strained five-membered cyclic sulfamides with excellent enantioselectivities. Detailed deuterium-labeling studies, together with DFT computation, have revealed an unprecedented mode of asymmetric induction that consists of enantiodifferentiative H-atom abstraction and stereoretentive radical substitution.

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

Discovery of 32993-05-8

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1 ,1 -Bis(ethynyl)biferrocene as a linking group for gold, ruthenium, and osmium fragments: synthesis, solid state structures, and electrochemical, UV-Vis, and EPR spectroscopical studies

A series of organometallic mono- and disubstituted bis(alkynyl)biferrocenes of type (LnMC?C)-(HC?C)bfc (LnM = (eta5-C5H5)(Ph3P)2RU (8a), (eta5-C5H5)(Ph3P) 2Os (8b), (eta5 -C5H5)(dppf)Ru (8c); bfc = 1,1 -biferrocenyl, ((eta5 -C5H 4)2Fe)2; dppf = 1,1 -bis(diphenyl)phosphanyl ferrocene, (eta5 -C5H4PPh2) 2Fe) and (LnMC?C)2bfc (LnM = (Ph3P)Au (6), (eta5 -C5H5)(Ph 3P)2Ru (9a), (eta5 -C5H 5)(Ph3P)2Os (9b), (eta5 -C 5H5)(dppf)Ru (9c)) have been synthesized from (HC?C)2bfc (4) with either (Ph3P)AuCl (5) in the presence of HNEt2/[CuI] (synthesis of 6) or LnMX (L nMX = (eta5 -C5H5)(Ph 3P)2RuCl (7a); (eta5 -C5H 5)(Ph3P)2OsBr (7b); (eta5 -C 5H5)(dppf)RuCl (7c)) together with [H4N]PF 6 and KOtBu (synthesis of 8 and 9), respectively. The structures of 6, 8b, 9a, 9b, and 9c in the solid state were determined by single-crystal X-ray structure analysis, showing unsymmetrical (8) or symmetrical geometries (6, 9), with almost eclipsed conformations or approximately midway positions between the fully eclipsed and the fully staggered conformation of the bfc cyclopentadienyl rings and with anti geometry of the linear ethynyl connecting units. UV-vis and NIR spectroscopic measurements suggest a weak interaction between the appropriate metal atoms. The associated radical cations were in situ generated by stepwise chemical oxidation and characterized by continuous wave electron paramagnetic resonance (EPR) investigations in X-band performed at low temperature.

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

Some scientific research about (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium

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Inhibitory effect of ethylene in ene-yne metathesis: The case for ruthenacyclobutane resting states

Reaction kinetics and mechanistic studies for ethylene-internal alkyne metathesis promoted by the phosphine-free initiator Ru1 (Piers’s catalyst) is described. The kinetic order of reactants and catalyst was determined. The effect of ethylene was studied at different solution concentrations using ethylene gas mixtures applied at constant pressure. Unlike earlier studies with the second-generation Grubbs complex, ethylene was found to show an inverse first-order rate dependence. Under catalytic conditions, a ruthenacyclobutane intermediate was observed by proton NMR spectroscopy at low temperature. Combined with the kinetic study, these data suggest a catalytic cycle involving a reactive LnRu=CH2 species in equilibrium with ethylene to form a ruthenacyclobutane, a catalyst resting state. Rates were determined for a variety of internal alkynes of varying substitution. Also, at low ethylene pressures, preparative syntheses of several 2,3-disubstituted 1,3-butadienes were achieved. Using the kinetic method, several phosphine-free inhibitors were examined for their ability to promote ethylene-alkyne metathesis and to guide selection of the optimal catalyst.

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