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Wingtip substituents tailor the catalytic activity of ruthenium triazolylidene complexes in base-free alcohol oxidation

A series of RuII (eta6-arene) complexes with 1,2,3-triazolylidene ligands comprising different aryl and alkyl wingtip groups have been prepared and characterized by NMR spectroscopy, microanalysis, and in one case by X-ray diffraction. All complexes are active catalyst precursors for the oxidation of alcohols to the corresponding aldehydes/ketones without the need of an oxidant or base as additive. The wingtip groups have a direct impact on the catalytic activity, alkyl wingtips providing the most active species while aryl wingtip groups induce lower activity. An N-bound phenyl group was the most inhibiting wingtip group due to cyclometalation. Arene dissociation was observed as a potential catalyst deactivation pathway.

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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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Bidentate carbenoid ester coordination in ruthenium(II) Schiff-base complexes leading to excellent levels of diastereo- and enantioselectivity in catalytic alkene cyclopropanation

Exceptionally high stereoselectivity (ee ? 98%, dr ? 99:1) in the cyclopropanation of alkenes with ethyl diazoacetate using a non-planar ruthenium(II) Schiff-base precatalyst is a result of eta2C, O binding of the carbenoid ester intermediate, according to DFT calculations.

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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 new mono-N-tosylated diamine ligands based on (R)-(+)-limonene and their application in asymmetric transfer hydrogenation of ketones and imines

A synthetic procedure leading to the preparation of a new family of enantiopure mono-N-tosylated-1,2-diamines derived from (R)-(+)-limonene is described. (+)-Limonene was transformed into the appropriate N-tosyl derivative using N-tosylaziridination based on chloramine-T trihydrate. Subsequent ring opening by sodium azide afforded the corresponding isomeric azides. Finally, reduction of the azide function gave enantiomerically pure mono-N-tosylated-1,2- diamines. The ligands obtained proved to be effective in the asymmetric transfer hydrogenation protocol on aromatic ketones and imines.

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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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Asymmetric hydrogenation of pro-chiral ketones catalyzed by chiral Ru(II)-benzene organometallic compounds containing amino acid based aroylthiourea ligands

A series of Ru(II)-benzene organometallic compounds (1?6) constructed from [RuCl2(eta6-benzene)]2and chiral aroylthiourea ligands (L1-L6) obtained from D/L-phenylalanine, was fully characterized. The chiral complexes along with 2-propanol and NaOH effected the asymmetric hydrogenation of aromatic ketones at 82?C within 8?10?h. The reduction reactions proceeded with excellent conversions and enantiomeric excesses (up to 99%).

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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, structure, and reactivity of RuII complexes with trimethylsilylethinylamidinate ligands

The mononuclear amidinate complexes [(eta6-cymene)-RuCl(1a)] (2) and [(eta6-C6H6)RuCl(1b)] (3), with the trimethylsilyl-ethinylamidinate ligands [Me3SiC?CC(N-c-C 6H11)2]- (1a-) and[Me3SiC?CC(N-i-C3H7)2] – (1b-) were synthesized in high yields by salt metathesis. In addition, the related phosphane complexes[(eta5- C5H5)Ru(PPh3)(1b)] (4a) [(eta5- C5Me5)Ru(PPh3)(1b)] (4b), and [(eta6-C6H6)Ru(PPh3)(1b)](BF 4) (5-BF4) were prepared by ligand exchange reactions. Investigations on the removal of the trimethyl-silyl group using [Bu 4N]F resulted in the isolation of [(eta6-C 6H6)Ru(PPh3){(N-i-C3H 7)2CC?CH}](BF4) (6-BF4) bearing a terminal alkynyl hydrogen atom, while 2 and 3 revealed to yield intricate reaction mixtures. Compounds 1a/b to 6-BF4 were characterized by multinuclear NMR (1H, 13C, 31P) and IR spectroscopy and elemental analyses, including X-ray diffraction analysis of 1b, 2, and 3. Copyright

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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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Asymmetrische Katalysen. LXXXII. Enantioselektive Hydrierung von 4-Oxoisophoron

Enantioselective hydrogenation of 4-oxoisophorone 1, catalysed by BINAP-RuII complexes, gives the corresponding saturated diketone 2 in 80percent chemical yield and 50percent enantiomeric excess.By repeated crystallisation from petroleum ether/dichloromethane 4/1 the diketone 2 is obtained optically pure in 25percent total yield.The monoalcohol 3 is formed as a byproduct of the hydrogenation.The formation of 3 can be suppressed by using the monomethyl-eol ether 4 as a substrate.Catalytic hydrogenation of 4 in methanol gives exclusively the dimethylketal 5, which upon acidic hydrolysis is transformed into the diketone 2 in 50percent ee.

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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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Electro-assembly of a chromophore-catalyst bilayer for water oxidation and photocatalytic water splitting

The use of electropolymerization to prepare electrocatalytically and photocatalytically active electrodes for water oxidation is described. Electropolymerization of the catalyst RuII(bda)(4-vinylpyridine)2 (bda=2,2?-bipyridine-6,6?-dicarboxylate) on planar electrodes results in films containing semirigid polymer networks. In these films there is a change in the water oxidation mechanism compared to the solution analogue from bimolecular to single-site. Electro-assembly construction of a chromophore-catalyst structure on mesoporous, nanoparticle TiO2 films provides the basis for a dye-sensitized photoelectrosynthesis cell (DSPEC) for sustained water splitting in a pH 7 phosphate buffer solution. Photogenerated oxygen was measured in real-time by use of a two-electrode cell design.

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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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Application of new Ru (II) pyridine-based complexes in the partial oxidation of n-octane

Tridentate and bidentate Ru (II) complexes were prepared through reaction of four pyridine-based ligands: pyCH2N(R)CH2py {R = propyl, tert-butyl, cyclohexyl and phenyl; py = pyridine} with the [(eta6-C6H6)Ru(mu-Cl)Cl]2 dimer. Crystal structures of the new terdentate Ru (II) complexes [Ru{pyCH2N(R)CH2py}C6H6](PF6)2 (R = C3H7 (1), C (CH3)3 (2), C6H11 (3) and the bidentate Ru (II) complex [Ru{pyCH2N(R)}C6H6]PF6 (R = C6H5 (4)) are reported. It was found that complexes 1, 2, 3 and 4 crystallised as mono-metallic species, with a piano stool geometry around each Ru centre. All complexes were active in the selective oxidation of n-octane using t-BuOOH and H2O2 as oxidants. Complexes 2 and 4 reached a product yield of 12% with t-BuOOH as oxidant, however, superior yields (23?32%) were achieved using H2O2 over all systems. The selectivity was predominantly towards alcohols (particularly 2-octanol) over all complexes using t-BuOOH and H2O2 after reduction of the formed alkylhydroperoxides in solution by PPh3. High TONs of up to 2400 were achieved over the Ru/H2O2 systems.

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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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Highly versatile heteroditopic ligand scaffolds for accommodating group 8, 9 & 11 heterobimetallic complexes

Two highly versatile xanthene scaffolds containing pairs of heteroditopic ligands were found to be capable of accommodating a range of transition metal ions, including Au(i), Ir(i), Ir(iii), Rh(i), and Ru(ii) to generate an array of heterobimetallic complexes. The metal complexes were fully characterised and proved to be stable in the solid and solution state, with no observed metal-metal scrambling. Heterobimetallic complexes containing the Rh(i)/Ir(i) combinations were tested as catalysts for the two-step dihydroalkoxylation reaction of alkynediols and sequential hydroamination/hydrosilylation reaction of alkynamines.

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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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Selective Complexation of Li+ in Water at Neutral pH Using a Self-Assembled Ionophore

A trinuclear metallamacrocycle was obtained by assembly of a tridentate ligand and a ruthenium complex in water at neutral pH. The complex acts as a potent ionophore for lithium ions with a Li+/Na+ selectivity of 10000:1. Copyright

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