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Studien zur C-H-Aktivierung IV. Inter- and Intra-molekulare C-H-Aktivierung mit Komplexfragmenten des Typs (M=Ru, Os)

The dihydro ruthenium and osmium complexes C6H6RuH2(PPri3), C6Me6RuH2 (R=Me, Pri) and C6H6OsH2(PPri3) can be obtained from the corresponding dihalogeno derivatives C6R6MX2(L) (X=Cl,I) and NaBH4 or Na.Photolysis, in presence of benzene and toluene, of C6H6RuH2(PPri3) or C6Me6RuH2(PMe3) gives the hydrido(phenyl) and hydrido(tolyl) complexes, C6H6RuH(C6H4R)(PPri3) or C6Me6RuH(C6H4R)(PMe3) (R=H, Me) in 35-63percent yield.C6H6RuH(C6H4Me)(PPri3) or C6Me6RuH(C6H4Me)(PMe3) can also be prepared from C6H6RuBr(C6H4Me)(PPri3) or C6Me6RuBr(C6H4Me)(PMe3) and NaBH4 in ethanol.Photolysis of C6H6RuH2(PPri3 ) in cyclohexane, hexane of mesitylene leads to the formation of the four-membered metallaheterocycle C6H6(H)RuCH2CH(CH3)PPi2<*> which can be isolated as a pair of diastereomers.It reacts smoothly with C6H6, C6D6 and C6H5Me in the dark to give the corresponding aryl(hydrido)ruthenium compounds C6H6RuH(C6H4R)(PPri3) (R=H, Me) and C6H6RuD(C6D5)(PPri3) in almost quantitative yield.In contrast to C6H6RuH2(PPri3), the corresponding osmium complex C6H6OsH2(PPri3) is photochemically inert.C6H6OsH(C6H5)(PPri3), C6H6OsH(C6H5)(PMe3) and C6H6OsD(C6D5)(PMe3) have been obtained from the reaction of C6H6OsI2(PR3) (R=Me, Pri) with NaC10H8 in THF/C6H6 or C6D6, by the classical Chatt route.

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

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In Situ routes to catalytically active Ru(0) Species by reduction of readily available, air-stable precursors

Cross-dimerization of a conjugated diene with a substituted alkene catalyzed by in situ reduction of an air-stable Ru(II) catalyst precursor has been achieved. Reaction of 2,3-dimethylbutadiene with styrene is catalyzed by [Ru(acac)2(eta4-1,5-COD)] (2a) (5 mol %) with BuLi (10 mol %) at 50 C for 6 h in hexane, giving the cross-dimers in 99% yield ((E)-4,5-dimethyl-1-phenylhexa-1,4-diene (3a)/(E)-4,5-dimethyl-1-phenylhexa-2,4-diene (3b)/isomers = 84/9/7). Because neither 2a nor BuLi separately catalyzes the cross-dimerization and reduction of 2a with BuLi in the presence of naphthalene produces [Ru(eta6-naphthalene)(eta4-1,5-COD)] (1a), the active species in this catalysis is considered to be a Ru(0) compound. Interestingly, this in situ reduction method of Ru(II) using BuLi can be applied to the cross-dimerization using an ester such as methyl acrylate. Alternatively, an air-stable Ru(II) complex having a labile arene ligand such as [RuCl2(eta6-anisole)]2 (5c) (5 mol %) with Na2CO3 (40 mol %) in the presence of 1,5-COD (20 mol %) at 100 C for 6 h in 2-butanol also catalyzes the same cross-dimerization in 62% yield. These protocols provide facile methods for production of unsaturated linear compounds by the cross-dimerization using air-stable Ru(II) catalyst precursors.

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

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Novel ruthenium-catalyzed cross-carbonylation of alkynes and 2-norbornenes to hydroquinones

Unsymmetrically substituted hydroquinones were obtained in high yields by the novel ruthenium-catalyzed cross-carbonylation of alkynes and 2-norbornenes. For example, treatment of 4-octyne and 2-norbornene with 2 mol % Ru3(CO)12 in N-methylpiperidine under 60 atm of carbon monoxide at 140C for 20 h gave the corresponding hydroquinone, 4,5-dipropyltricyclo[6.2.1.02,7]undeca-2(7),3,5-triene-3,6-diol, in 85% yield. The reaction apparently involves a maleoylruthenium intermediate which is generated by the reaction of an alkyne and two molecules of carbon monoxide on the ruthenium.

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

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Synthesis and characterization of half-sandwich ruthenium(II) complexes with N-alkyl pyridyl-imine ligands and their application in transfer hydrogenation of ketones

A series of new arene ruthenium(II) complexes were prepared by reaction of ruthenium(II) precursors of the general formula [(eta6-arene)Ru(mu-Cl)Cl]2 with N,N?-bidentate pyridyl-imine ligands to form complexes of the type [(eta6-arene)RuCl(C5H4N-2-CH=N-R)]PF6, with arene?=?C6H6, R?=?iso-propyl (1a), tert-butyl (1b), cyclohexyl (1c), cyclopentyl (1d) and n-butyl (1e); arene?=?p-cymene, R?=?iso-propyl (2a), tert-butyl (2b). The complexes were fully characterized by 1H NMR and 13C NMR, UV?Vis and IR spectroscopies, elemental analyses, and the single-crystal X-ray structures of 2a and 2b have been determined. The single-crystal molecular structure revealed both compounds with a pseudo-octahedral geometry around the Ru(II) center, normally referred to as a piano stool conformation, with the pyridyl-imine as a bidentate N,N ligand. The activity of all complexes in the transfer hydrogenation of cyclohexanone in the presence of NaOH and iso-propanol is reported, the compounds showing turnover numbers of close to 1990 and high conversions. Complex 2b was also shown to be very effective for a range of aliphatic and cyclic ketones, giving conversions of up to 100?%.

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

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Mononuclear complexes of platinum group metals containing eta6- And eta5cyclic II-perimeter hydrocarbon and pyridylpyrazolyl derivatives: Syntheses and structural studies

Piano-stool-shaped platinum group metal compounds, stable in the solid state and in solution, which are based on 2-(5-pheny1-1H-pyrazol-3-yl)pyridine (L) with the formulas [(eta6-arene)Ru(L)C1]PR6{arene= C6H6 (1),p-cymene (2), and C6Me6, (3)}, [(eta6-C5Me5)M(L)C1]PF6 {M = Rh (4), Ir (5)}, and [(eta5-C5H5) Ru(TPPh3)(L)]PF6 (6), [(eta5-C 5.H5)Os(PPh3)(L)]PF6 (7), [(eta5-C5Me5)Ru(PPh3)(L)]PF 6 (8), and [(eta5-C9H7)Ru(PPh 3)-(L)]PF6 (9) were prepared by a general, method, and characterized by NMR and IR spectroscopy and mass spectrometry. The molecular structures of compounds 4 and 5 were established by single-crystal X-ray diffraction. In each compound the metal is connected to N1 and N11 in a k 2 manner.

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

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Enantioselective Cyanosilylation of Alkynyl Ketones Catalyzed by Combined Systems Consisting of Chiral Ruthenium(II) Complex and Lithium Phenoxide

Asymmetric cyanosilylation of alkynyl ketones with the catalyst systems consisting of amino acid/2,2?-bis(diphenylphosphino)-1,1?-binaphthyl (BINAP)/ruthenium(II) complex and lithium phenoxide (Ru?Li cat.) was studied. The reaction was conducted in tert-butyl methyl ether (TBME) at ?78 C with a substrate-to-catalyst molar ratio (S/C) as high as 2000. A series of simple and functionalized ketones was converted into the alkynyl tertiary cyanohydrin derivatives in up to 99% ee. Appropriate selection of an amino-acid ligand of the catalyst according to the substrate structure was crucially important to achieve high enantioselectivity and a wide scope of substrates. Transformation of the chiral cyanohydrin product into a functionalized lactone was also examined. (Figure presented.).

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

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DIPHOSPHINE LIGAND AND TRANSITION METAL COMPLEX USING THE SAME

The present invention provides a novel ligand represented by the following formula and a novel transition metal complex having the ligand, which shows superior enantioselectivity and catalytic efficiency, particularly high catalyst activity, in various asymmetric synthesis reactions. A transition metal complex having, as a ligand, a compound represented by the formula wherein R4 is a hydrogen atom or a C1-6 alkyl group optionally having substituent(s), and R5 and R6 are each a C1-6 alkyl group optionally having substituent(s), or the formula is a group represented by the formula wherein ring B is a 3- to 8-membered ring optionally having substituent (s).

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

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A simple method for asymmetric trifluoromethylation of N-acyl oxazolidinones via Ru-catalyzed radical addition to zirconium enolates

A Ru-catalyzed direct thermal trifluoromethylation and perfluoroalkylation of N-acyloxazolidinones has been developed. The reaction is experimentally simple and requires inexpensive reagents while providing good yields of products with good levels of stereocontrol. Preliminary studies have shown notable compatibility with functional groups, aromatics, and certain heteroaromatic substituents. The described method provides a useful alternative for the synthesis of fluorinated materials in an experimentally convenient manner.

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

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Ruthenium complexes containing bis(diarylamido)/thioether ligands: Synthesis and their catalysis for the hydrogenation of benzonitrile

Treatment of the thioethers (RNH-o-C6H4)2S (H2[R2NSN]; R = Xy, Xyf; Xy = 3,5-Me2C6H3, Xyf = 3,5-(CF3)2C6H3) with 2 equiv of n-BuLi followed by addition of 0.5 equiv of [(eta6-C6H6)RuCl2]2 in THF gave the bis(diarylamido)/thioether complexes [(eta6-C6H6)Ru[R2NSN]] (R = Xy (1a), R = Xyf (1b)) in moderate yields. In the presence of 1a (1 mol %) and PCy3 (2 mol %; Cy = cyclohexyl), benzonitrile was catalytically hydrogenated to give benzylamine (72%) and benzylidenebenzylamine (27%) at 80 C and 30 atm, while the hydrogenation with 1b as a catalyst precursor resulted in the formation of benzylamine (37%) and benzylidenebenzylamine (51%) under the same reaction conditions. The yield of benzylamine was improved up to 92% by using a catalyst mixture of 1a (1 mol %)/PCy3 (2 mol %)/t-BuONa (10 mol %). On the other hand, the reaction of la with excess PMe3 afforded the tris(trimethylphosphine) derivative [(PMe3)3Ru[Xy2NSN]] (2). Treatment of 2 with excess PhCN, MeCN, or N2H4¡¤H2O resulted in the replacement of a PMe3 ligand by these substrates to give [(PMe3)2LRu[Xy2NSN]] (3, L = PhCN; 4, L = MeCN; 5, L = N2H4), while the reaction of 2 with benzoylhydrazine gave the kappa2-benzoylhydrazido complex [(PMe3)2Ru(kappa2-(O,N)-PhC(O)= NNH2)(H[Xy2NSN])] (6). Structures of 1a, 1b, 2, 5, and 6 have been determined by X-ray crystallography.

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

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Atom- and Step-Economical Ruthenium-Catalyzed Synthesis of Esters from Aldehydes or Ketones and Carboxylic Acids

We developed a ruthenium-catalyzed reductive ester synthesis from aldehydes or ketones and carboxylic acids using carbon monoxide as a deoxygenative agent. Multiple factors influencing the outcome of the reaction were investigated. Best results were obtained for commercially available and inexpensive benzene ruthenium chloride; as low as 0.5 mol % of the catalyst is sufficient for efficient reaction. Competitive studies demonstrated that the presence of even 1000 equiv of alcohol in the reaction mixture does not lead to the corresponding ester, which clearly indicates that the process is not a simple reductive esterification but a novel type of Ru-catalyzed redox process.

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