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Catalytic isomerization of allylic alcohols promoted by complexes [RuCl2(eta6-arene)(PTA-Me)] under homogeneous conditions and supported on Montmorillonite K-10

The mononuclear arene-ruthenium(II) derivatives [RuCl2(eta 6-arene)(PTA-Me)] (arene = C6H6 (3a), p-cymene (3b), 1,3,5-C6H3Me3 (3c), C6Me 6 (3d)), containing the ionic phosphine ligand 1-methyl-3,5-diaza-1- azonia-7-phosphaadamantane chloride (PTA-Me), have been synthesized and fully characterized. These complexes were evaluated as potential catalysts for the redox isomerization of allylic alcohols. Among them, best results in terms of activity were obtained with complex [RuCl2(eta6-C 6H6)(PTA-Me)] (3a) which, in combination with K 2CO3 (2.5 equiv. per Ru), was able to selectively isomerize a number of allylic alcohols RCH(OH)CHCH2 (R = H, aryl, alkyl or heteroaryl group) into the corresponding carbonyl compounds RC(O)CH2CH3 in refluxing THF (TOF values up to 800 h -1). Complex [RuCl2(eta6-C6H 6)(PTA-Me)] (3a) was adsorbed onto the Montmorillonite K-10 clay, and the resulting solid proved also active in the isomerization of the model substrate 1-octen-3-ol. In addition, it could be easily separated from the reaction media by simple filtration and reused several times (up to 11 consecutive runs) with retention of its efficiency.

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

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Water Oxidation by Ruthenium Complexes Incorporating Multifunctional Bipyridyl Diphosphonate Ligands

We describe herein the synthesis and characterization of ruthenium complexes with multifunctional bipyridyl diphosphonate ligands as well as initial water oxidation studies. In these complexes, the phosphonate groups provide redox-potential leveling through charge compensation and sigma donation to allow facile access to high oxidation states. These complexes display unique pH-dependent electrochemistry associated with deprotonation of the phosphonic acid groups. The position of these groups allows them to shuttle protons in and out of the catalytic site and reduce activation barriers. A mechanism for water oxidation by these catalysts is proposed on the basis of experimental results and DFT calculations. The unprecedented attack of water at a neutral six-coordinate [RuIV] center to yield an anionic seven-coordinate [RuIV?OH]?intermediate is one of the key steps of a single-site mechanism in which all species are anionic or neutral. These complexes are among the fastest single-site catalysts reported to date.

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

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Complete chiral induction from enantiopure 1,2-diamines to benzophenone-based achiral bisphosphane ligands in noyori-type RuII catalysts

We report the design and synthesis of a novel class of RuII catalysts (3) composed of achiral benzophenone-based bisphosphane ligands and enantiopure 1,2-diamines for the asymmetric hydrogenation of aryl ketones. The developed catalysts show excellent enantioselectivities (up to 97 % ee) and activities (up to S/C = 10,000) in the hydrogenation of a variety of aromatic ketones. Complete chiral induction from the enantiopure 1,2-diamine to the achiral bisphosphane ligand was observed. The coordination of the C=O moiety in 3 to the cationic RuII center is considered to be of key importance in providing a higher thermodynamic and kinetic rotation barrier for the flexible bisphosphane ligand, resulting in the preferential formation of only one diastereomer, and thus explaining the high enantioselectivity of the catalyst. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.

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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 tris(heteroleptic) Ru(II) complexes bearing styryl subunits

We have developed and optimized a well-controlled and refined methodology for the synthesis of substituted pi-conjugated 4,4?-styryl-2,2?- bipyridine ligands and also adapted the tris(heteroleptic) synthetic approach developed by Mann and co-workers to produce two new representative Ru(II)-based complexes bearing the metal oxide surface-anchoring precursor 4,4?-bis[E-(p-methylcarboxy-styryl)]-2,2?-bipyridine. The two targeted Ru(II) complexes, (4,4?-dimethyl-2,2?-bipyridine)(4, 4?-di-tert-butyl-2,2?-bipyridine)(4,4?-bis[E-(p-methylcarboxy- styryl)]-2,2?-bipyridine) ruthenium(II) hexafluorophosphate, [Ru(dmbpy)(dtbbpy)(p-COOMe-styryl-bpy)](PF6)2 (1) and (4,4?-dimethyl-2,2?-bipyridine)(4,4?-dinonyl-2, 2?-bipyridine)(4,4?-bis[E-(p-methylcarboxy-styryl)]-2, 2?-bipyridine) ruthenium(II) hexafluorophosphate, [Ru(dmbpy)(dnbpy)(p- COOMe-styryl-bpy)](PF6)2 (2) were obtained as analytically pure compounds in high overall yields (>50% after 5 steps) and were isolated without significant purification effort. In these tris(heteroleptic) molecules, NMR-based structural characterization became nontrivial as the coordinated ligand sets each sense profoundly distinct magnetic environments greatly complicating traditional 1D spectra. However, rational two-dimensional approaches based on both homo- and heteronuclear couplings were readily applied to these structures producing quite definitive analytical characterization and the associated methodology is described in detail. Preliminary photoluminescence and photochemical characterization of 1 and 2 strongly suggests that both molecules are energetically and kinetically suitable to serve as sensitizers in energy-relevant applications.

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

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Catalytic Asymmetric Intermolecular Cyclopropanation of a Ketone Carbene Precursor by a Ruthenium(II)-Pheox Complex

The diazo derivative of acetonyl acetate is a useful basic skeleton for the synthesis of cyclopropyl ketones. The intermolecular cyclopropanations of diazo acetoxy acetone with olefins are accomplished by using a novel p-nitro-Ru(II)-diphenyl-Pheox catalyst to give the corresponding optically active cyclopropane derivatives in good yields (up to 95%) with excellent diastereoselectivities (up to 99:1) and enantioselectivities (up to 98% ee). (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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Dual-targeting organometallic ruthenium(ii) anticancer complexes bearing EGFR-inhibiting 4-anilinoquinazoline ligands

We have recently demonstrated that complexation with (eta6-arene)RuII fragments confers 4-anilinoquinazoline pharmacophores a higher potential for inducing cellular apoptosis while preserving the highly inhibitory activity of 4-anilinoquinazolines against EGFR and the reactivity of the ruthenium centre to 9-ethylguanine (Chem. Commun., 2013, 49, 10224-10226). Reported herein are the synthesis, characterisation and evaluation of the biological activity of a new series of ruthenium(ii) complexes of the type [(eta6-arene)Ru(N,N-L)Cl]PF6 (arene = p-cymene, benzene, 2-phenylethanol or indane, L = 4-anilinoquinazolines). These organometallic ruthenium complexes undergo fast hydrolysis in aqueous solution. Intriguingly, the ligation of (arene)RuII fragments with 4-anilinoquinazolines not only makes the target complexes excellent EGFR inhibitors, but also confers the complexes high affinity to bind to DNA minor grooves while maintaining their reactivity towards DNA bases, characterising them with dual-targeting properties. Molecular modelling studies reveal that the hydrolysis of these complexes is a favourable process which increases the affinity of the target complexes to bind to EGFR and DNA. In vitro biological activity assays show that most of this group of ruthenium complexes are selectively active inhibiting the EGF-stimulated growth of the HeLa cervical cancer cell line, and the most active complex [(eta6-arene)Ru(N,N-L13)Cl]PF6 (4, IC50 = 1.36 muM, L13 = 4-(3?-chloro-4?-fluoroanilino)-6-(2-(2-aminoethyl)aminoethoxy)-7-methoxyquinazoline) is 29-fold more active than its analogue, [(eta6-arene)Ru(N,N-ethylenediamine)Cl]PF6, and 21-fold more active than gefitinib, a well-known EGFR inhibitor in use clinically. These results highlight the strong promise to develop highly active ruthenium anticancer complexes by ligation of cytotoxic ruthenium pharmacophores with bioactive organic molecules.

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

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Thermal study of areneruthenium(II) derivatives

The TG and DTG study of areneruthenium(II) derivatives [Ru(arene)Cl2L] (arene = benzene or p-cymene (p-MeC6H4CHMe2); L = aniline, diethylamine, dimethylsulfoxide, tetrahydrothiofene or dimethylsulfide) was carried out under a dynamic air atmosphere. The kinetics of the first step of thermal decomposition were evaluated from the dynamic weight loss data by means of Coats-Redfern, MacCallum-Tanner and Horowitz-Metzger methods. The Dn and Rn models were selected as the models best fitting the experimental TG curves. The values of activation energy, E, and frequency factor, A, of the thermal decomposition were calculated.

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

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Selective Preparation of a Heteroleptic Cyclometallated Ruthenium Complex Capable of Undergoing Photosubstitution of a Bidentate Ligand

Cyclometallated ruthenium complexes typically exhibit red-shifted absorption bands and lower photolability compared to their polypyridyl analogues. They also have lower symmetry, which sometimes makes their synthesis challenging. In this work, the coordination of four N,S bidentate ligands, 3-(methylthio)propylamine (mtpa), 2-(methylthio)ethylamine (mtea), 2-(methylthio)ethyl-2-pyridine (mtep), and 2-(methylthio)methylpyridine (mtmp), to the cyclometallated precursor [Ru(bpy)(phpy)(CH3CN)2]+ (bpy=2,2?-bipyridine, Hphpy=2-phenylpyridine) has been investigated, furnishing the corresponding heteroleptic complexes [Ru(bpy)(phpy)(N,S)]PF6 ([2]PF6?[5]PF6, respectively). The stereoselectivity of the synthesis strongly depended on the size of the ring formed by the Ru-coordinated N,S ligand, with [2]PF6 and [4]PF6 being formed stereoselectively, but [3]PF6 and [5]PF6 being obtained as mixtures of inseparable isomers. The exact stereochemistry of the air-stable complex [4]PF6 was established by a combination of DFT, 2D NMR, and single-crystal X-ray crystallographic studies. Finally, [4]PF6 was found to be photosubstitutionally active under irradiation with green light in acetonitrile, which makes it the first cyclometallated ruthenium complex capable of undergoing selective photosubstitution of a bidentate ligand.

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

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Homo- and Hetero-binuclear Complexes containing the Anion 2(pyrazolate)>- as Ligand. Crystal Structure of <(C5Me5)Rh2(mu-C3H3N2)Ru(C6H6)>ClO4*CH2Cl2

The neutral rhodium(III) complex > reacts with pyrazole-type ligands in the presence of AgClO4 yielding cationic complexes of the general formula (HL)>ClO4.They react with Na2CO3 in aqueous solutions with formation of the neutral complexes 2(HL)>.Addition of NaH in tetrahydrofuran to the cationic complexes or thallium acetylacetonate in MeOH to the neutral compounds affords the corresponding bimetallic derivatives <(C5Me5)Rh2LM> (M = Na or Tl).These complexes react with halide compounds such as <2> , , <(PtMe3I)4> or <2> (cod = cycloocta-1,5-diene) to give cationic or neutral complexes of the type <(C5Me5)Rh2(mu-L)M(ring)>ClO4 or <(C5Me5)Rh2(mu-L)MLn> .The crystal structure of <(C5Me5)Rh2(mu-pz)Ru(C6H6)>ClO4*CH2Cl2 has been determined by X-ray diffraction methods: monoclinic, space group P21/c, a = 11.179(1), b = 17.039(1), c = 18.186(2) Angstroem, beta = 94.85(1) deg and Z = 4.The complex cation consists of one rhodium and one ruthenium atom bridged by two phosphonate and one pyrazolate anion.An eta5-C5Me5 and an eta6-C6Me6 group complete the co-ordination spheres of the metals, which show no direkt intermetallic interaction.

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

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Cationic half-sandwich Ru(II) complexes containing (N,N)-bound Schiff-base ligands: Synthesis, crystal structure analysis and spectroscopic studies

Three Ru(II) half-sandwich complexes containing (N,N)-bound Schiff-base ligands, [(eta6-C6H6) RuCl(L1)]PF6 (1) L1 = (E)-1-(6-methylpyridin-2-yl)-N-(p-tolyl)methanimine, [(eta6-p-cymene)RuCl(L1)]PF6 (2) and [(eta6-p-cymene)RuCl(L2)]PF6 (3) L2 = (E)-1-(6-bromopyridin-2-yl)-N-(p-tolyl)methanimine, were synthesized, characterized and their supramolecular structures were analyzed. The crystal packing of these compounds was studied using geometrical analysis and Hirshfeld surface analysis. The fluorescence behavior of these compounds was also studied. TD-DFT calculations were carried out to better understand the fluorescence properties of complexes 1-3. These compounds could be promising for the design of organometallic dye systems.

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