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The use of 3,3-bis(2-imidazolyl) propionic acid (bip-OH) as a new chelating ligand for Re(CO)3 and Ru complexes: Formation of organometallic PNA oligomers with (bip)Re(CO)3 and their interaction with complementary DNA

We report the use of 3,3-bis(2-imidazolyl) propionic acid (bip-OH, 1) as a new chelating bis(imidazole) ligand. The synthesis and full characterization of complexes Re(bip-O)(CO)3 2 and [Ru(bpy)2(bip-OH)] 2+ 3 is reported. Both complexes show interesting spectroscopic properties, namely IR for compound 2 and 1H NMR for 3, respectively. The free carboxylic acid functionality of 1 may be used for the coupling to biomolecules. We have prepared two peptide nucleic acid (PNA) decamers to which the rhenium complex 2 is coupled. All reactions were carried out by solid phase synthesis methods. The Re-PNA oligomer conjugates Re(CO)3(bip- tgt cta gca a -NH2) 4 and Re(CO)3(bip- agg agc aac t-Lys-NH2) 5 were obtained in good yield and high purity after HPLC purification and identified by their mass spectra. The interaction of 5 with complementary DNA yields a melting temperature of (53.9 ¡À 1)C. This is the first DNA melting temperature reported for an organometallic metal-PNA conjugate.

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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 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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Reference£º
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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Redox transformations of bis(2,2?-bipyridine)(1-methyl-1-pyridin-2- yl-ethylamine)ruthenium(II)

The amineruthenium(II) complex Ru(bpy)2(mpea)2+ has been prepared by the direct reaction of 1-methyl-1-pyridin-2-yl-ethylamine (mpea) with Ru(bpy)2Cl2 in ethanol/water and isolated as the hexafluorophosphate salt. Electrochemical analysis of this complex shows that it undergoes sequential one-electron oxidations to an amidoruthenium(III) intermediate (E? = 1.086 V vs NHE) and then to an amidoruthenium(IV) (E? = 0.928 V) or imidoruthenium(IV) (E? = 1.083 V) complex, depending upon the solution pH (pKa = 2.62 for the amidoruthenium(IV) species). At higher potentials (Epa = 1.5 V in 1.0 M H2SO4), the amido- or imidoruthenium(IV) species is irreversibly oxidized to the corresponding nitrosoruthenium(II) complex. The mechanism for this transformation appears, on the basis of b3lyp/cpcm/cep-31g(d) computations, to proceed through an imidoruthenium(V) intermediate, which is rapidly attacked by water to yield a Ru(II)-bound hydroxylamine radical, which is readily oxidized and deprotonated to produce the nitrosoruthenium(II) complex. The nitrosoruthenium(II) complex is quantitatively reduced to the original [Ru(bpy)2(mpea)]2+ complex at relatively negative potentials (Epc = -0.2 V in 1.0 M H2SO4).

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

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Photosensitizing metal-organic framework enabling visible-light-driven proton reduction by a wells-dawson-type polyoxometalate

A simple and effective charge-assisted self-assembly process was developed to encapsulate a noble-metal-free polyoxometalate (POM) inside a porous and phosphorescent metal-organic framework (MOF) built from [Ru(bpy)3]2+-derived dicarboxylate ligands and Zr6(mu3-O)4(mu3-OH)4 secondary building units. Hierarchical organization of photosensitizing and catalytic proton reduction components in such a POM@MOF assembly enables fast multielectron injection from the photoactive framework to the encapsulated redox-active POMs upon photoexcitation, leading to efficient visible-light-driven hydrogen production. Such a modular and tunable synthetic strategy should be applicable to the design of other multifunctional MOF materials with potential in many 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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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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Reference£º
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