Oxidation of Alcohols Catalyzed by Ruthenium Complexes with Iodosylbenzene as Oxidant

Five ruthenium complexes such as Phen-Ru-Phen, Phen-Ru-Bipy, Phen-Ru-Quin, Quin-Ru-Quin and Bipy-Ru-Quin (where Phen=1, 10-phenanthroline, Quin=8-hydroxyquinoline, Bipy=2, 2′-bipyridine) were synthesized and used as catalysts for the oxidation of benzylic and primary aliphatic alcohols with iodosylbenzene as oxidant. The oxidations were carried out at room temperature, affording the corresponding aldehydes and ketones with high selectivity.

New Ruthenium Complexes of Fullerene C60&C70

The new complexes [Ru(NO)(PPh3)]2(h2-Cm)(m=60 1 or 70 2) have been prepared by heating a solution of C60(or C70) with [Ru(NO)2(PPh3)2] in toluene. They have been characterized by elemental analysis, IR, UV/VIS, XPS, 13C and 31P NMR spectroscopy. The photovaltaic effect for the new compounds has been studied.

Half-sandwich Ruthenium Complexes with Naphthalene-based Schiff Base Ligands:Syntheses,Characterization and Catalytic Activities for the Reduction of Nitroarenes

Three half-sandwich ruthenium（II） p-cymene complexes containing naphthalenebased Schiff base ligands [Ru（p-cymene）LCl]（2 a～2 c） have been synthesized and characterized. Both Schiff-base ligands and ruthenium complexes were fully characterized by ^1H and ^13C NMR spectra, mass spectrometry and infrared spectrometry. The molecular structure of ruthenium complex 2 b was confirmed by single-crystal X-ray diffraction methods. For the complex： C（24H23ClN2ORu, Mr = 524.02, monoclinic, space group P21/c, a = 12.3888（4）, b = 17.3296（6）, c = 20.7744（7）A°, β = 92.8000（10）°, V = 4454.8（3） A°^3, Z = 8, Dc = 1.563 g/cm^3, μ = 0.936 mm^-1, F（000） = 2128, S = 1.154, the final R = 0.0309 and w R = 0.0703. Moreover, these ruthenium complexes are active catalysts for the hydrogenation of nitroarenes to aromatic anilines in the presence of sodium tetrahydroborate（NaBH4） reducing agent.

Electronic Structures, DNA-binding, SAR, and Spectral Properties of Ruthenium Methylimidazole Complexes [Ru（MeIm）4L]^2＋（L=iip,tip,2ntz）

Theoretical studies on the electronic and geometric structures, the trend in DNA-binding affinities as well as the the structure-activity relationship （SAR） of a series of water-soluble Ru（II） methylimidazole complexes, i.e. [Ru（Mehn）4iip]^2＋ （1） （MeIm=l-methylimidazole, iip=2-（1H-imidazo-4-group）-lH-imidazo[n,5-f][1,10]phenanthroline）, [Ru（MeIm）4tip]^2＋ （2） （tip=2-（thiophene-2-group）-lH-imidazo[4,5-f] [i,10]phenanthroline）, and [Ru（Melm）42ntz]^2＋ （3） （2ntz=2-（2-nitro-l,3-thiazole-5-group）-lH-imidazo[4,5-f][1,10]phenanthroline）, were car- ried out using the density functional theory （DFT）. The electronic structures of these Ru（II） complexes were analyzed on the basis of their geometric structures optimized in aqueous solution, and the trend in the DNA-binding constants （Kb） was reasonably explained. The results show that the replacement of imidazole ligand by thiophene ligand can effectively improve the DNA-binding affinity of the complex. Meanwhile, it was found that introduc- ing the stronger electronegative N atom and NO2 group on terminal loop of intercalative ligand can obviously reduce the complex＇s LUMO and HOMO-LUMO gap energies. Based on these findings, the designed complex [Ru（MeIm）42ntz]^2＋ （3） can be expected to have the greatest Kb value in complexes 1-3. In addition, the structure-activity relationships and antitumor mechanism were also carefully discussed, and the antimetastatic activity of the designed complex 3 was predicted. Finally, the electronic absorption spectra of this series of complexes in aqueous solution were calculated, simulated and assigned using DFT/TDDFT methods as well as conductor-like polarizable continuum model （CPCM）, and were in good agreement with the experimental results.

Electropolymerized films of redox-active ruthenium complexes for multistate near-infrared electrochromism,ion sensing,and information storage

This paper summarizes our recent progress on the preparations and applications of electropolymerized thin films of redox-active ruthenium complexes.Thin films of vinyl-functionalized diruthenium or ruthenium-amine conjugated complexes are prepared by reductive electropolymerization.The resulting films are useful for multistate near-infrared electrochromism,ion sensing,and mimicking flip-flop and flip-flap-flop logic gates.The oxidative electropolymerization of diruthenium complexes with two distal triarylamine units affords electropolymers with an alternating diruthenium and tetraphenylbenzidine structural unit.The applications of the resulting films in multistate near-infrared electrochromism and resistive memory are discussed.

Synthesis and Characterization of Ferroceneterminated Ruthenium Phenylacetylide Complexes with Alligator Clips

Ferrocene-terminated trans-Ru(dppm)2 (dppm=Ph2PCH2PPh2)-containing molecular wires with alligator clips were prepared. They are suitable for self-assembly on gold electrode to investigate the influence of metal incorporation on the electron transportation property of the molecular wires.

Asymmetric hydrogenation of aromatic ketones using new chiral-bridged diphosphine/diamine-Ru(Ⅱ) complexes

A series of chiral secondary alcohols were easily prepared by means of asymmetric hydrogenation of prochiral aromatic ketones using a new（（Rax）-BuP）/（R,R）-DPEN-Ru（Ⅱ） complex catalyst system.The hydrogenation of 2-methylacetophenone in n-butanol （t-BuOK/Ru =45.6/1,S/C = 500,20 atm.of H2,20℃,48 h） afforded（S）-1-（2＇-methylphenyl）ethanol in 92%ee and〉99% conversion.

Electrogenerated chemiluminescence sensor for the determination of metoclopramide using ordered mesoporous carbon for immobilizing tris(2,2'-bipyridyl)ruthenium

A novel electrogenerated chemiluminescence(ECL)sensor for the determination of metoclopramide was developed by employing ruthenium complex as an ECL signal producer and an ordered mesoporous carbon(OMC)material as modified material.The ECL sensor was fabricated by adsorption ruthenium complex into a mixture of OMC and Nafion,which showed good electrochemical and ECL behaviors.It was found that the ECL intensity of the sensor fabricated was greatly enhanced in the presence of metoclopramide.Based on this finding,a highly sensitive and reproducible ECL method was developed for the determination of metoclopramide.The result showed that the ECL intensity was linear with the concentration of metoclopramide in the range from 1.0×10-10 to 5.0×10-7M and the detection limit was 3×10-11M.The ECL sensor exhibited a long-term stability and a fine reproducibility with relative standard deviation of 1.0 % for 1.0×10-10M metoclopramide in 18 continuous determinations.The developed method has been applied to the determination of metoclopramide in tablet samples with satisfactory results.

Synthesis and Photochemical Properties of a New Substituted Phenol Covalently Linked to Ruthenium (Ⅱ) Tris-bipyridine Containing Four Ester Groups as Sensitizer

As photosensitizer for solar cell, a new ruthenium (Ⅱ) complex with four ester groups hadbeen synthesized, in which a phenol substituted by {[(2-hydroxy-5-tert-butylbenzyl)(pyridyl-2-methyl)amino]methyl} is covalently linked to ruthenium (Ⅱ) tris-bipyridine. The structures ofthe new compounds were confirmed by NMR and ESI-MS spectra. The electrochemical andphotochemical properties were also studied.

Highly efficient oxidation of alcohols using Oxone~ as oxidant catalyzed by ruthenium complex under mild reaction conditions

Aromatic and alkyl alcohols were oxidized to the corresponding aldehydes or ketones at room temperature with high conversion and selectivity using Oxone （2KHSOs-KHSO4.K2SO4） as oxidant catalyzed by ruthenium complex Quin-Ru-Quin （where Quin = 8-hydroxyquinoline）. The reaction time is very short and the preparation of complex is simple.

Enantioselective Transfer Hydrogenation of Aromatic Ketones Catalyzed by New Diaminodiphosphine Ru(Ⅱ) Complexes

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Synthesis and Structural Characterization of a Ruthenium Complex:trans-RuCl_2(COD)Py_2

A new ruthenium complex trans-RuCl2（COD）Py2 has been synthesized and characterized by elemental analysis, IR, IH NMR and single-crystal X-ray diffraction. Crystal data： trans- RuCl2（COD）Py2, Mr = 438.35, monoclinic, space group P21/c, a = 8.9116（9）, b = 14.6175（15）, c = 13.7582（14）A, β = 101.994（1）°, V= 1753.1（3）A^3, Z= 4, Dc= 1.661 g/cm^3, F（000）= 888,μ = 1.199 mm^-1, R = 0.0376 and wR = 0.0789 for 2492 observed reflections with I 〉 2σ（I）.

Synthesis and Catalytic Activity of a Two-core Ruthenium Carbene Complex: a Unique Catalyst for Ring Closing Metathesis Reaction

The reaction of a ruthenium carbide complex RuCl2（C：）（PCy3）2 with [H（Et2O）x]＋[BF4]- at a molar ratio of 1：2 produced a two-core ruthenium carbene complex, {[RuCl（=CHPCy3）（PCy3）]2（μ-Cl）3}＋·[BF4]-, in the form of a yellow-green crystalline solid in a yield of 94%. This two-core ruthenium complex is a selective catalyst for ring closing metathesis of unsubstituted terminal dienes. More importantly, no isomerized byproduct was observed for N-substrates when the two-core ruthenium complex was used as the catalyst at an elevated temperature（137 °C）, indicating that the complex is a chemo-selective catalyst for ring closing metathesis reactions.

Dissolved oxygen sensor based on sol-gel matrix doped with tris(2,2'-bipyridine)ruthenium dichloride

To establish a immobilization method of oxygen sensitive dye, a dissolved oxygen sensor based on a sol-gel matrix doped with ruthenium complex ([Ru(bpy)3]2+) as the oxygen-sensitive material is reported. The results indicate that the I0 /I100 value of the [Ru(bpy)3]2+-doped in tetraethylorthosilane (TEOS) composite films are estimated to be 10.6, where I0 and I100 correspond to the detected fluorescence intensities in pure nitrogen saturated water and pure oxygen saturated water, respectively. Also, the Stern-Volmer plot shows a very good linearity at low dissolved oxygen concentrations. The response time of the composite films is 5 s upon switching from nitrogen saturated water to oxygen saturated water and 10 s from oxygen saturated water to nitrogen saturated water. The dissolved oxygen sensors based on the ruthenium complex/TEOS composite films exhibit greater sensitivity, stability and faster response time as compared to the existing ones. Furthermore, the thin films possess greatly minimized dye leaching effect.

^(99)Ru and ^(13)C-NMR Spectra for the Tris Chelates of 5-Substituted 1,10-Phenanthrolines with Ruthenium (Ⅱ)

13C and 99Ru-NMR chendcal shifts are reported for the ruthenium(II) tris complexes of5-substitUted 1,10-phenanthrolines. It has been found that both of them are affected by the substituents on the phenanthrolines in a direction consistent with that expected from the electron withdrawing ability of the substituent.

A Ternary Ruthenium（II） 2,2′ ：6′,2″-Terpyridine Complex Having Intramolecular Tr-Tr Stacking Interaction with Ancillary Benzyl Groups of the Mixed Ligand

A new ruthenium（II） complex with two different types oftridentate ligands was synthesized, 2,2′：6′,2″-terpyridine （tpy） and 2,6-Bis（（N-benzyl）aminomethyl）pyridine （bbap）： [Ru（tpy）（bbap）]2＋ （1）. This compound was designed to form intramolecular π-π stacking interaction between tpy and substituted benzyl groups of bbap. The single-crystal X-ray diffraction analysis revealed that 1 crystallized with orthorhombic space group Aea2 and the ruthenium center has a distorted octahedral coordination geometry with fully chelated tpy and bbap ligands. Simultaneously, in the crystal structure of 1, the central part of ligating tpy was stacked and sandwiched with a pair of capped benzyl substituent groups of bbap, the nearest atomic distance being N...C = 3.28 A.

Syntheses,Crystal Structures and Magnetic Studies of Heterobimetallates Based on Paramagnetic Ruthenium(Ⅲ) Building Block [Ru~Ⅲ(salchda)(CN)2]

The syntheses, crystal structures and magnetic properties of two cyano-bridged heterobimetallic compounds prepared from a paramagnetic Ru^Ⅲ building block, transK[Ru^Ⅲ（salchda）（CN）2]（1, salchda = N,N＇-bis（salicylidene）-o-cyclohexylenediamine）, are described.1 reacts with hydrated CoCl2 and [Mn Ⅲ（salchda）（Cl）（H2O）] in MeOH to produce a trinuclear compound {[Ru^Ⅲ（salchda）（CN）]2（μ-CN）2[Co（MeOH）4]·4MeOH}n（2） and a dinuclear{[Ru^Ⅲ（salchda）（CN）]（μ-CN）[Mn^Ⅲ（salchda）（MeOH）]·2MeOH}n（3）, respectively. Both compounds exhibit intramolecular ferromagnetic coupling between Ru^Ⅲ and 3-d metal centers via the cyano bridge and intermolecular antiferromagnetic coupling. Moreover, 2 exhibits antiferromagnetic ordering below 3.4 K.

Designing macrophage membrane-engineered ruthenium/selenium nanoparticles to block bone metastasis of breast cancer

Bone metastasis along with osteolysis is a common complication of advanced breast cancer,which directly destroys bone function and becomes one of the major causes of cancer-related mortality.It is crucial to develop a new strategy to achieve effective cancer therapy and inhibition of osteolytic bone metastasis.Metal ruthenium(Ru)complexes exhibit therapeutic potential in cancer chemotherapy.However,the clinical applications of Ru complexes were limited by poor bioavailability,lacking targeting,nonspecific distribution.Therefore,in this study,engineering of cell membrane biomimetic modification was used to construct a highly biocompatible nanoplatform with carrying Ru metal complex of RuPOP and Se nanoparticles(SeNPs).Strikingly,the obtained RPSR nanoparticles can efficiently inhibit the proliferation,invasion and migration of breast cancer cells(MDA-MB-231 cells)in vitro.More importantly,RPSR nanoparticles can induce cycle arrest,apoptosis by generating excessive intracellular(reactive oxygen species,ROS)to disrupt the normal redox balance and induce DNA damage in tumor cells.Furthermore,RPSR nanoparticles can also reshape bone microenvironment by regulating selenoproteins to inhibit osteoclasts and avoid osteolytic bone metastasis induced by tumor development.Taken together,this study not only provides an effective cell membrane biomimetic strategy to enhance the shortcomings of metal complexes,but also demonstrates potential clinical significance for the combined treatment of anti-cancer and bone metastasis inhibition.

Directly Knitted Ruthenium Pincer Complexes with Enhanced Activity as Recyclable Single-Site Catalysts for Hydrogenation of CO_(2)to Methanol

Considering the importance of the valorization of CO_(2),a number of phosphine-containing ruthenium pincer complexes have been successfully heterogenized using a“direct knitting”strategy without any premodification.The resulting porous organometallic polymers(POMPs)with high specific-surface areas,hierarchical pores,and uniformly dispersed Ru single-sites exhibited outstanding catalytic activity toward the N-formylation of diverse amines with CO_(2).Besides excellent turnover number(TON,5×10^(5))and turnover frequency(TOF,5592 h-1),the obtained formamides were readily hydrogenated to methanol with the same catalyst.Consequently,an amine-assisted direct hydrogenation system of CO_(2)to methanol was established by POMPs with higher activity and TON(1.46×10^(4))than their molecular precursors,shedding light on the direct valorization of CO_(2)and carbon neutral recycling.

二炔基桥联双核钌配合物的电喷雾质谱研究

A rapid method is applied to analyze conjugated organic ligands bridged binuclear ruthenium complexes by electrospray ionization-tandem mass spectrometry (ESI MSn).Fragmentation pattern be discussed.