Ru Cl Research Articles

Investigation of short-term chemical changes in stable ruthenium added to soil by using X-ray absorption fine-structure analysis.

Radioactive ruthenium may be accidentally released from spent nuclear fuel reprocessing plants to the surrounding environment. However, research on the chemical behavior of radioactive Ru in the environment is limited, and the complex chemical properties of this element complicate the application of extraction methods for the analyses of its chemical forms. To obtain basic information regarding the outcome of radioactive Ru in the environment, we investigated the changes in the form of stable Ru added to soil through X-ray absorption fine-structure (XAFS) analysis. This study uses ruthenium tetroxide (RuO4), ruthenium dioxide (RuO2), ruthenium nitrosyl nitrate (Ru(NO)(NO3)3) and ruthenium chloride (RuCl3) as test sources. These are added to ultrapure water, soil solution or fresh soil samples, which are analyzed using XAFS immediately or 5 days after Ru addition. The Ru K-edge X-ray absorption near edge structure spectra acquired immediately after Ru addition differed with respect to the source. The XAFS results suggest that RuO4 immediately changes to tetravalent form after deposition from air to soil. For RuCl3, the ionic structure in the vicinity of Ru is affected by the soil even if the valence does not change immediately. By contrast, RuO2 and Ru(NO)(NO3)3 are highly stable in soil. The results show that the chemical forms of RuO2 and Ru(NO)(NO3)3 added to the soil solution and soil are retained for 5 days, whereas those of RuCl3 and RuO4 are affected by the soil solution and soil within a short period. These results emphasize the need to focus on the chemical form of Ru deposits and the form change after Ru addition when investigating the environmental fate of radioactive Ru.

Electronically Weakly Coupled 4,4′‐Divinylazoarylenes‐Bridged Diruthenium Complexes Featuring Two Ru(CO)Cl(PiPr3)2 Entities

AbstractWe report here on four novel 4,4′‐divinylazoarylenes‐bridged diruthenium complexes featuring two Ru(CO)Cl(PiPr3)2 entities with a general formula of [{Ru(CO)Cl(PiPr3)2}2(μ‐{CH=CH−Ar}2‐N=N‐4,4′)]; Ar=C6H4; [1 azo], C6H3‐2‐Me; [2 azo], C6H3‐(Me)2‐2,6; [3 azo], and C6H2‐(iPr)2‐2,6; [4 azo]. Those five‐coordinated, square‐pyramidal, 16‐valence electrons (VEs) type‐complexes [1 azo]–[4 azo] were successfully synthesized by the stereo‐and regiospecific insertion of the Ru−H bond of the hydrido substrate HRu(CO)Cl(PiPr3)2 into the two terminal acetylenic bonds of the corresponding 4,4′‐diethynylated azoarylenes [L1]–[L4]. They were routinely characterized in their neutral state by traditional IR, UV/Vis and NMR spectroscopic techniques, and in their two‐closely accessible oxidized states by IR, UV/Vis/NIR spectroelectrochemistry along with electrochemical techniques as well as by (TD)‐DFT calculations. Detailed electrochemical studies on these complexes and IR, UV/Vis/NIR spectro(electro)scopic characterization of their oxidized forms along with (TD)‐DFT calculations revealed to massive 4,4′‐divinylazobenzene linker contributions to the two redox processes in addition to the noteworthy negligible electronic interaction “communication” between the two remote redox‐active end‐groups, rendering them as unique weakly coupled borderline class I/II MV systems in accordance with the Robin and Day classification. Incorporating the four bulky iPr substituents into the ortho‐positions of the 4,4′‐divinylazobenzene linker results to a significant decrease in the tendency of the co‐planarity of the bridge.

Electrochemiluminescence Biosensor for Ascorbic Acid Based on Target Transformation of Cell-Free RNA Transcription System and Duplex-Specific Nuclease-Assisted Recycling Amplification.

A cell-free RNA transcription system had been coupled with electrochemiluminescence (ECL) detection technology for the first time to develop an ascorbic acid (AA, acting as a model target) biosensor. The biosensor is composed of single-stranded DNA (ssDNA) sequences modified with alkynyl and azido groups, respectively, alongside an incomplete gene circuit framework. The addition of target AA and copper ions will cause the linkage of the two ssDNA sequences through a click chemistry reaction. This results in the subsequent reconstruction of a complete gene circuit. The reconstituted gene circuit, in conjunction with the T7 RNA polymerase, drives the transcription of substantial quantities of RNA. ssDNA labeled with ferrocene (Fc) (Fc-DNA) had been immobilized on a tris(2,2'-bipyridyl) ruthenium(II) chloride hexahydrate-doped SiO2 nanoparticle (Ru@SiO2 NPs) modified electrode first. The quenching effect of Fc on Ru@SiO2 causes the low ECL detected. The transcribed RNA sequence assisted double-stranded specific nuclease (DSN) to cut the ssDNA-Fc and the ECL of the system was enhanced. Optimal experimental conditions reveal that the ECL signal exhibits a linear correlation with the logarithmic concentration of AA, spanning a detection range from 100 nM to 1 mM, with a detection limit of 45 nM. This innovative methodology expands the utility of a cell-free RNA transcription system within the realm of biosensing applications.

Metal Ruthenium Complexes Treat Spinal Cord Injury By Alleviating Oxidative Stress Through Interaction With Antioxidant 1 Copper Chaperone Protein.

Oxidative stress is a major factor affecting spinal cord injury (SCI) prognosis. A ruthenium metal complex can aid in treating SCI by scavenging reactive oxygen species via a protein-regulated mechanism to alleviate oxidative stress. This study aimed to introduce a pioneering strategy for SCI treatment by designing two novel half-sandwich ruthenium (II) complexes containing diverse N^N-chelating ligands. The general formula is [(η6-Arene)Ru(N^N)Cl]PF6, where arene is either 2-phenylethanol-1-ol (bz-EA) or 3-phenylpropanol-1-ol (bz-PA), and the N^N-chelating ligands are fluorine-based imino-pyridyl ligands. This study shows that these ruthenium metal complexes protect neurons by scavenging reactive oxygen species. Notably, η6-Arene substitution from bz-PA to bz-EA significantly enhances reactive oxygen species scavenging ability and neuroprotective effect. Additionally, molecular dynamics simulations indicate that the ruthenium metal complex increases Antioxidant 1 Copper Chaperone protein expression, reduces oxidative stress, and protects neurons during SCI treatment. Furthermore, ruthenium metal complex protected spinal cord neurons and stimulated their regeneration, which improves electrical signals and motor functions in mice with SCI. Thus, this treatment strategy using ruthenium metal complexes can be a new therapeutic approach for the efficient treatment of SCI.

A synergetic effect of light and anion: near-infrared colorimetric monitoring of nitric oxide (NO) release from fluoride/cyanide anions and a water responsive ruthenium nitrosyl complex.

Near-infrared (NIR) spectral-responsive multitasking chemical systems are always advantageous in biological and environmental systems. Although ruthenium complexes are highly attractive compounds for many applications, studies on NIR optical responsive sensors are very limited because of their synthetic difficulties. The sensing of fluoride and cyanide ions using ruthenium nitrosyl complexes is not known. In this study, we report the synthesis and characterization of a new terpyridine-based ruthenium nitrosyl complex [Ru(Cl)2NO(terpy-C6H4OH)] 1·Ru-OH. The complex exhibited distinct NIR absorptions at 680 nm, as well as a visible color change with the fluoride ion in DMSO-CH3CN medium. However, when the solvent is changed to DMSO-H2O, it responds only with a cyanide ion with a distinct colorimetric change. Binding of the F- ion leads to deprotonation of 1·Ru-OH; the deprotonated complex is also used for the colorimetric detection of a trace amount of water in DMSO and acetonitrile with a limit of detection (LOD) of 0.034 wt% and 0.007 wt%, respectively. Ruthenium nitrosyl complexes have appeared as promising platforms for light-controlled release of nitric oxide (NO), which can be beneficial for therapeutic application. NO release studies of 1·Ru-OH by UV-vis and FT-IR spectroscopy confirm that it can release NO in a light-controlled manner. In addition, the NO release could be monitored by the naked eye with a color change and spectral change in the NIR region. Importantly, NO release studies revealed that the rate of NO release could be modulated in the presence of the F- ion. Here, the fluoride ion acts as an allosteric regulator. These results demonstrate that 1·Ru-OH is both a promising multitasking colorimetric and NIR sensor and a colorimetric responsive NO-releasing agent.

Reusable fluorescence nanoprobe based on DNA-functionalized metal-organic framework for ratiometric detection of mercury (II) ions.

Areusable fluorescent nanoprobewas developedusing DNA-functionalized metal-organic framework (MOF) for ratiometric detection of Hg2+. We utilized a zirconium-based MOF (UiO-66) to encapsulate tris(bipyridine) ruthenium(II) chloride (Ru(bpy)32+), resulting in Ru(bpy)32+@UiO-66 (RU) with red fluorescence. The unsaturated metal sites in UiO-66 facilitate the attachment of thymine-rich single-strand DNA (T-ssDNA) through Zr-O-P bond, producing T-ssDNA-functionalized RU complex (RUT). The T-ssDNA selectively binds to Hg2+, forming stable T-Hg2+-T base pairs and folding into double-stranded DNA, which permits the intercalation of SYBR Green I (SGI) and activates its green fluorescence. In the presence of Hg2+, SGI fluorescence increases in a dose-dependent manner, while Ru(bpy)32+ fluorescence remains constant. This fluorescence contrast enables RUT to serve as an effective ratiometric nanoprobe for Hg2+ detection, with a detection limit of 3.37 nM. Additionally, RUT demonstrates exceptional reusability due to the ability of cysteine to remove Hg2+, given its stronger affinity for thiol groups. The RUT was successfully applied to detect Hg2+ in real water samples. This work advances the development of ratiometric fluorescence nanoprobe based on DNA-functionalized MOFs.

Ringing the Changes: Effects of Heterocyclic Ring Size on Stereoselectivity in [(η5-C5Me5)RhCl], [(η5-C5Me5)IrCl] and [Ru(η6-cymene)Cl] Complexes of Chiral 3-Amino-1-Azacycles.

Ring size-dependent diastereoselective coordination of unsymmetrical diamines containing one azacyclic nitrogen and one exocyclic nitrogen to [(η5-C5Me5)MCl]+ cores where M = Rh, Ir and [Ru(η6-cymene)Cl]+ is reported herein. Total stereoselectivity was observed with the six- and seven-membered azacycles, whereas the five-derivative proved poorly selective. All complexes were active for transfer hydrogenation but showed no enantioselectivity with prochiral ketones.

Ruthenium-doped dual-phase cobalt catalysts for enhanced electrocatalytic hydrogen evolution

Controlling the structural sensitivity and selectivity of metal catalysts in reactions, such as the hydrogen evolution reaction (HER) on cobalt crystals, remains a challenging issue in heterogeneous catalysis. In this study, we introduced a straightforward approach to tuning the phase composition of hexagonal close-packed cobalt (HCP-Co) and face-centered cubic cobalt (FCC-Co) in a core–shell Co/C catalyst through the incorporation of Ru atoms. The HER performance was evaluated by controlling the contents of HCP-Co and FCC-Co phases in the catalysts. Single-atom Ru-doped cobalt catalysts containing dual-phase HCP and FCC were prepared by a mechanical ball-milling zeolitic imidazolate framework (ZIF-67) with appropriate ruthenium chloride, followed by a pyrolysis process. The doping of Ru resulted in changes in the contents of the HCP-Co and FCC-Co phases, which significantly boosted the HER activity of the catalysts. The obtained biphasic Ru-Co/C catalyst demonstrated ultra-low HER overpotential and promising stability in alkaline and acidic media, outperforming single-phase cobalt and commercial Pt/C catalysts. Theoretical calculations revealed the synergistic catalysis effect of biphasic cobalt on HER. These findings, which indicated that significant activity dependence on the crystallographic structure, may inspire new design concepts for efficient metal electrocatalysts.

Red‐Emitting Pyrazole Azo Hydrazone and Its Metal Complexes for Photophysical Probing, Latent Fingerprints, Anti‐counterfeiting, and Biological Studies

ABSTRACTThe present paper discusses the synthesis of unprecedented red‐emitting mono‐azo compound pyrazole azo fluorescent tag (PAFT) by a diazotization method, followed by an electrophilic substitution reaction. Further, the metal complex of PAFT is also prepared by refluxing the ethanolic solution of the ligand with the corresponding metal (RuCl3 and C4H6CuO4.H2O) salts under suitable experimental conditions. The synthesized fluorophore PAFT displays intense fluorescence in the aggregate state and has excellent qualities, including high purity, low cost, eco‐friendliness, and good photostability. These unique characteristics of PAFT led to the development of new fluorescence‐based technology for the in situ viewing of latent fingerprints. Various spectroscopic and analytical techniques are used to confirm the structural characteristics of the synthesized compounds, including UV–Vis, FT‐IR, (1H) NMR, HRMS, TGA, VSM, ESR, and powder XRD methods. The potency of the antibacterial activity of the compounds was evaluated. The results revealed that compound PAFT and [Ru(PAFT)Cl3] H2O showed excellent sensitivity at 0.8 μL/mL against the Gram‐positive bacteria Staphylococcus aureus.

Solvent-free oxidation of alcohols by a heterogeneous Fe3O4@SiO2-DTPA-Ru nanocatalyst

A novel magnetic heterogeneous ruthenium catalyst (Fe3O4@SiO2-DTPA-Ru) was prepared by using magnetic silicon spheres as support, ethylenediaminepentaacetic acid (DTPA) as functional ligands, ruthenium chloride as catalyst precursor. The results obtained after a series of characterizations showed that the catalyst Fe3O4@SiO2-DTPA-Ru was 5–15 nm in size with a 0.205 nm lattice and contained 0.31 mmol Ru/g catalyst. It also had a good thermal stability under 232°C which was verified by thermal filtration method. Besides, the saturation magnetic intensity was as high as 20.54 emu/g. The catalyst Fe3O4@SiO2-DTPA-Ru was applied for the first time into thirteen oxidation reactions of aromatic alcohols and showed good catalytic activity even the yields of eleven aromatic alcohols were all over 90%. In catalyzing 1-phenylethanol to acetophenone, its TOF and TON were 9677 h−1 and 6991, respectively. The Fe3O4@SiO2-DTPA-Ru catalyst could still maintain good reusability and catalytic performance after 15 cycles of 1-phenylethanol oxidation, which was superior to many reported catalysts and had great potential in future industrial production.

Ruthenium(III) unsymmetrical Schiff base complex supported on γ-Fe2O3 magnetic nanoparticles: A new heterogeneous nanocatalyst for efficient oxidation of hydrocarbons with tert-butyl hydroperoxide

In the present work, an unsymmetrical salen-type ruthenium(III) complex, Ru(salenac)Cl, where the unsymmetrical tetradentate Schiff base H2salenac = salicylideneiminoethyliminopentane-2-one, was synthesized and anchored on the surface of aminopropyl-functionalized silica-coated γ-Fe2O3 magnetic nanoparticles. The characterization of the resulting γ-Fe2O3@SiO2@APTES@Ru(salenac)Cl nanoparticles was performed using XRD, FT-IR, VSM, TGA, ICP, TEM, BET, SEM and EDX methods. The prepared γ-Fe2O3@SiO2@APTES@Ru(salenac)Cl magnetic nanoparticle was successfully employed as an efficient heterogeneous nanocatalyst for alkenes epoxidation and alkanes oxidation with tert-butyl hydroperoxide (tert-BuOOH, 70 % aqueous solution) as oxidant in acetonitrile at ambient temperature. In the mentioned catalytic system, the intended products were obtained with good to excellent yields along with high selectivity. The heterogeneous γ-Fe2O3@SiO2@APTES@Ru(salenac)Cl nanocatalyst can be recovered easily using an external magnet and recycled six times with no notable decrease in catalytic activity. Moreover, FT-IR, XRD, SEM and EDX techniques were used to characterize the recovered γ-Fe2O3@SiO2@APTES@Ru(salenac)Cl nanocatalyst and it was demonstrated that the catalyst maintained its structure intact following the recovery process.

Aloe vera gel mediated green synthesis of ruthenium nanoparticles and their potential anticancer activity

Metal nanoparticles have a noteworthy future in cancer treatment research because of their smaller size and large active surface area. Though gold, silver, platinum, palladium, copper, zinc, iron and several other metal nanoparticles have been explored for their anticancer potential in different pathways, the main limitation of these particles is their toxicity which may be controlled through their size, surface modification and route of administration. Compared to other metal nanoparticles, ruthenium nanoparticles have high bio compatibility and they exhibit excellent photo-thermal effect. Though there are several reports in the literature on the anticancer potential of ruthenium complexes, ruthenium nanoparticles are not much investigated. In the present work, therefore, an attempt has been made to synthesize ruthenium nanoparticles in an easy and eco-friendly way using Aloe vera gel. Ruthenium chloride was used as a precursor and Aloe vera gel acted both as reducing and capping agent. The synthesized ruthenium nanoparticles were characterized using UV-Visible spectrophotometry, Fourier Transform Infrared Spectroscopy (FT-IR), High Resolution Transmission Electron Microscopy (HRTEM), Powder X-ray Diffraction (PXRD), Dynamic Light Scattering (DLS) and Field Emission Scanning Electron Microscopy (FESEM). The analyses confirmed the formation of nano globules of Aloe vera gel of diameter in the range 90–300 nm with ruthenium nanoparticles of average size 1.5 nm embedded in them. The synthesized Ru nanoparticles embedded in the nano globules of Aloe vera gel (ALV RuNPs) were explored for their anticancer potential in the Dalton's lymphoma ascites (DL) cell line using Trypan Blue assay. The results of the assay showed that the ALV RuNPs can induce concentration dependent cytotoxicity in DL cancer cells. Approximately 40 % cytotoxicity was obtained for concentration range 5–50 mg/mL of the sample while negligible cytotoxicity was observed for healthy PBMC cells. Theoretical study indicates significant interaction between the components present in Aloe vera and Ru-nanoparticles. The results showed that ruthenium nanoparticles can emerge as a promising bio-compatible candidate with the ability to selectively target cancer cells while sparing normal cells.

(η6-Benzene)-chlorido-[(S)-2-(4-isopropyl-4,5-di-hydro-oxazol-2-yl)phenolato]ruthenium(II).

The title compound, [Ru(C12H14NO2)Cl(η6-C6H6)], exhibits a half-sandwich tripod stand structure and crystallizes in the ortho-rhom-bic space group P212121. The arene group is η6 π-coordinated to the Ru atom with a centroid-to-metal distance of 1.6590 (5) Å, with the (S)-2-(4-isopropyl-4,5-di-hydro-oxazol-2-yl)phenolate chelate ligand forming a bite angle of 86.88 (19)° through its N and phenolate O atoms. The pseudo-octa-hedral geometry assumed by the complex is completed by a chloride ligand. The coordination of the optically pure bidentate ligand induces metal centered chirality onto the complex with a Flack parameter of -0.056.

Immobilising ruthenium organosilane complexes on ITO electrode surface towards electrogenerated chemiluminescence

A light-emitting organosilane molecule based on a Ru-complex was synthesized from 1,10-phenanthroline, (3-Aminopropyl)triethoxysilane (APTES), ruthenium trichloride, and 2,2′-Bipyridine. The resulting complex was covalently attached to a transparent conductive substrate, Indium-Tin Oxide (ITO), using a straightforward dipping method. Surface characterization of the modified substrates was conducted through X-ray photoelectron spectroscopy (XPS) and electrochemical experiments, confirming the presence of covalent bonds. The immobilized film of the ruthenium organosilane complex on ITO demonstrated robust stability as a modified electrode and holds significant promise as a novel light-emitting material.

Arene ruthenium(II) complexes with 3-acetyl coumarin derivatives bearing a 3-hydroxy-2-naphthoic hydrazide moiety: Synthesis, DFT calculations and antioxidant studies

The reaction of [(arene)RuCl2]2 with coumarin hydrazone ligands in methanol yielded neutral chelating mononuclear N∩O metal complexes having the general formula [(arene)Ru(L)Cl] where arene = p-cymene, benzene; and L = 3‑hydroxy-N'-(1-(2-oxo-2H-chromen-3-yl)ethylidene)-2-naphthohydrazide (L1), 3‑hydroxy-N'-(1-(7‑methoxy-2-oxo-2H-chromen-3-yl)ethylidene)-2-naphthohydrazide (L2), (E)-N'-(1-(6‑bromo-2-oxo-2H-chromen-3-yl)ethylidene)-3‑hydroxy-2-naphthohydrazide (L3) and 3‑hydroxy-N'-(1-(3-oxo-3H-benzo[f]chromen-2-yl)ethylidene)-2-naphthohydrazide (L4)}. All complexes (1–8) were fully characterized by spectroscopic techniques like IR, UV–Vis, NMR and ESI-MS spectral methods. The solid-state molecular structures of the three complexes were determined using a single-crystal X-ray diffraction study. The studies revealed that the ligands binding mode to the ruthenium metal centers is through the azomethine nitrogen and the imidolate oxygen forming a five-membered chelating ring. All the complexes and the ligands were screened for antibacterial and antioxidant activity studies. Some of the complexes exhibited antioxidant activity that is more prominent than their respective ligands.

A green and pollution-free heterogeneous ruthenium catalyst anchoring on magnetic nanoparticles with FPBA and DTPA groups for oxidation of aromatic alcohols

Using ruthenium chloride as catalyst precursor, magnetic silicon spheres as support, 4-formylphenylboronic acid and ethylenediaminepentaacetic acid as functional ligands, a magnetic heterogeneous nano-ruthenium catalyst (Fe3O4@SiO2-FPBA-DTPA-Ru) was prepared for the first time. It was nano level with 20.17 emu/g saturation magnetic strength and thermal stability under 249.63 °C. Fe3O4@SiO2-FPBA-DTPA-Ru contained 0.38 mmol/g Ru and was successfully used to catalyze the oxidation reactions of 15 aromatic secondary alcohols. Results proved that Fe3O4@SiO2-FPBA-DTPA-Ru as catalyst had good catalytic activity for the oxidation of secondary aromatic alcohols with yields exceeding 90 % for 12 products and 95 % for 10 products. High TON and TOF values (6386 and 9158 h−1) in 1-phenylethanol oxidation were obtained. All the reactions of aromatic alcohols were carried out in a solvent-free system, so the prepared catalyst had the characteristics of green and pollution-free. It was’nt suitable for oxidation of aromatic primary alcohols. If there was steric hindrance around the hydroxyl group in substrate, the catalysis also may be limited. The Fe3O4@SiO2-FPBA-DTPA-Ru catalyst also exhibited the advantages of energy saving, satisfactory reusability and stability in 9 consecutive runs. It showed great potential for future large-scale industrial production.

Synthesis of quinazolinone derivatives with a seven‐membered ring using borrowing hydrogen methodology

In this study, we synthesized 23 quinazolinone derivatives with the seven-membered C-ring through intramolecular borrowing hydrogen reaction of 3-(3-hydroxypropyl)-2-(1H-indol-2-yl)-quinazolin-4(3H)-one, in yields ranging from 31 % to 68 %. The reaction took place in the presence of cesium carbonate and DMF, using triphenylphosphine ruthenium chloride (PPh3)3RuCl2 as a catalyst and Xantphos as a ligand. Water was the only byproduct. Furthermore, pharmacological activity tests were conducted on these compounds, revealing that some of the products exhibited anti-inflammatory and anticancer properties.

Phosphate-Buffered Saline and Dimethyl Sulfoxide Enhance the Antivenom Action of Ruthenium Chloride against Crotalus atrox Venom in Human Plasma-A Preliminary Report.

Ruthenium chloride (RuCl3) is widely utilized for synthesis and catalysis of numerous compounds in academia and industry and is utilized as a key molecule in a variety of compounds with medical applications. Interestingly, RuCl3 has been demonstrated to modulate human plasmatic coagulation and serves as a constituent of a compounded inorganic antivenom that neutralizes the coagulopathic effects of snake venom in vitro and in vivo. Using thrombelastography, this investigation sought to determine if RuCl3 inhibition of the fibrinogenolytic effects of Crotalus atrox venom could be modulated by vehicle composition in human plasma. Venom was exposed to RuCl3 in 0.9% NaCl, phosphate-buffered saline (PBS), or 0.9% NaCl containing 1% dimethyl sulfoxide (DMSO). RuCl3 inhibited venom-mediated delay in the onset of thrombus formation, decreased clot growth velocity, and decreased clot strength. PBS and DMSO enhanced the effects of RuCl3. It is concluded that while a Ru-based cation is responsible for significant inhibition of venom activity, a combination of Ru-based ions containing phosphate and DMSO enhances RuCl3-mediated venom inhibition. Additional investigation is indicated to determine what specific Ru-containing molecules cause venom inhibition and what other combinations of inorganic/organic compounds may enhance the antivenom effects of RuCl3.

New half-sandwich ruthenium(II) complexes of chelating (SS) organochalcogen ligands and their application as transfer hydrogenation catalysts

Room temperature reactions of [(η6-arene)Ru(μ-Cl)Cl]2 (arene = p-cymene) with three new bidentate (SS) organochalcogen ligands, 2a–c (2a: 1,1’-ethylenebis(3-ethyl-imidazole-2-thione), 2b: 1,1’-ethylenebis(3-propyl-imidazole-2-thione), 2c: 1,1’-methylenebis(3-ethyl-imidazole-2-thione)), and in situ anionic exchange with KPF6 afforded the corresponding new 18-electron half-sandwich [(η6-arene)RuLCl]PF6 complexes 3a–c (3a: L = 2a, 3b: L = 2b, 3c: L = 2c). The Ru(II) complexes and the organochalcogen ligands were fully characterized by spectroscopic and analytical techniques. Solid state single crystal X-ray diffraction analysis of 3a–c displayed the Ru(II) center in the expected piano stool geometry. The catalytic activities of the half-sandwich ruthenium complexes toward the transfer hydrogenation of ketones to their corresponding alcohols were investigated using 2-propanol as a hydrogen source and solvent. All three Ru(II) complexes exhibited excellent catalytic activity for the transfer hydrogenation of ketones in the order 3b > 3a > 3c at an appreciably low catalyst loading of 0.5 mol% under a minimal alkaline condition of 10 mol% KOH. The catalytic activities of the complexes are influenced by the length of the alkyl spacer and the steric bulk of the N-substituents on the chelating organochalcogen ligand framework.

Photocatalytic Conversion of CO2 to Formate/CO by an (η6-para-Cymene)Ru(II) Half-Metallocene Catalyst: Influence of Additives and TiO2 Immobilization on the Catalytic Mechanism and Product Selectivity.

The catalytic efficacy of the monobipyridyl (η6-para-Cymene)Ru(II) half-metallocene, [(p-Cym)Ru(bpy)Cl]+ was evaluated in both mixed homogeneous (dye + catalyst) and heterogeneous hybrid systems (dye/TiO2/Catalyst) for photochemical CO2 reduction. A series of homogeneous photolysis experiments revealed that the (p-Cym)Ru(II) catalyst engages in two competitive routes for CO2 reduction (CO2 to formate conversion via RuII-hydride vs CO2 to CO conversion through a RuII-COOH intermediate). The conversion activity and product selectivity were notably impacted by the pKa value and the concentration of the proton source added. When a more acidic TEOA additive was introduced, the half-metallocene Ru(II) catalyst leaned toward producing formate through the RuII-H mechanism, with a formate selectivity of 86%. On the other hand, in homogeneous catalysis with TFE additive, the CO2-to-formate conversion through RuII-H was less effective, yielding a more efficient CO2-to-CO conversion with a selectivity of >80% (TONformate of 140 and TONCO of 626 over 48 h). The preference between the two pathways was elucidated through an electrochemical mechanistic study, monitoring the fate of the metal-hydride intermediate. Compared to the homogeneous system, the TiO2-heterogenized (p-Cym)Ru(II) catalyst demonstrated enhanced and enduring performance, attaining TONs of 1000 for CO2-to-CO and 665 for CO2-to-formate.