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Abstract: Structure elucidation plays a critical role across the landscape of medicinal chemistry, including medicinal inorganic chemistry. Herein, we discuss the importance of structure elucidation in drug development and then provide three vignettes that capture key instances of its relevance in the development of biologically active inorganic compounds. In the first, we describe the exploration of the biological activity of the trinuclear Ru compound called ruthenium red and the realization that this activity derived from a dinuclear impurity. We next explore the development of Au‐based antitubercular and antiarthritic drugs, which features a key step whereby ligands were discovered to bind to Au through S atoms. The third exposition traces the development of As‐based antiparasitic drugs, a key step of which was the realization that the reaction of arsenic acid and aniline does not produce an anilide of arsenic acid, as originally thought, but rather an amino arsonic acid. These case studies provide the motivation for an outlook in which the development of Sb‐based antiparasitic drugs is described. Although antileishmanial pentavalent antimonial drugs remain in widespread use to this day, their chemical structures remain unknown.

A diaminocyclopentadienone ruthenium complex allows control of regioselectivity in the ruthenium-catalyzed isomerization of propargyl alcohols through the choice of additive. Thereby, both products of the Meyer–Schuster rearrangement and redox isomerization products are selectively accessible. In the presence of hydroxylamine- O -sulfonic acid, unsaturated nitriles are formed instead. The ruthenium catalyst is readily available and stable to moisture, air, and acidic conditions. [ABSTRACT FROM AUTHOR]

Ru/HAP catalyst with high-dispersion is prepared by a novel homogeneous deposition precipitation method (DPU). As compared to the conventional impregnation method (IM), the catalytic oxidation performance for toluene and DCM are much higher for DPU-sample with higher activity and good stability in humid air. Characterizations reveal that DPU-sample has a larger surface area with mesoporous structure, keeping smaller Ru particle size and uniform distribution on HAP, which is favorable for the exposure of active sites. The preparation and reaction conditions were also systematically studied, showing that 0.5 Ru/HAP(500)-DPU sample is a promising catalyst for VOC and CVOC removal. The Ru/HAP (DPU) is a promising broad-spectrum catalyst for VOC and CVOC removal. [ABSTRACT FROM AUTHOR]

In this study, we present the successful application of new and known stable 16‐electron ruthenium(II) pincer complexes POCOP, based on the naphthoresorcinate backbone, [Ru(X)(POCOP)(CO)] (X = H, Cl, Br, I, OCOCF3), in the catalytic alkylation of ketones and the coupling between amines and primary alcohols under mild conditions. These protocols demonstrated tolerance to a wide range of alcohols, ketones, and anilines, with reactions proceeding in high conversions and selectivity towards the hydrogenated ketones and the imines. The use of an excess of alcohol as the proton source facilitated the formation of the hydrogenated products. These results mark a significant advancement in the development of catalytic reactions with ruthenium POCOP pincer derivatives. [ABSTRACT FROM AUTHOR]

[Display omitted] Catalysts composed of nanocluster and single-atom (SA) were extensively used to enhance electrocatalytic water splitting performance, whereas study of their photocatalytic hydrogen (H 2) evolution activity was limited. Herein, carbon nitride (CN) decorated by ruthenium (Ru) cocatalysts existed as SA + cluster, cluster + nanoparticles (NPs), and NPs were prepared by impregnation and calcination processes. The correlation between existential form, content of Ru cocatalyst and H 2 evolution rate were carefully discussed. It was found that Ru NPs were favor for water molecule adsorption, whereas Ru SAs and clusters facilitated H 2 desorption. Theoretical calculations revealed that Ru clusters + NPs cocatalyst were beneficial for H* intermediate formation. Water splitting tests found that 1.07 wt% Ru NPs + cluster modified CN showed the highest H 2 evolution rate of 13.64 mmol h−1 g−1, which was 266.4 and 1.5 times higher than those of CN and Ru NPs (2.33 wt%) decorated CN, respectively. This work deeply reveals the influences of existential form of Ru cocatalysts on photocatalytic water splitting of CN, and provides thought in designing new cocatalysts to largely enhance H 2 evolution. [ABSTRACT FROM AUTHOR]

Half‐sandwich Ru(II)‐ and Os(II)‐arene complexes have great potential for catalytic and biological applications. The possibility of fine‐tuning their chemical reactivity by including modifications in the ligands around the metal adds to their many advantages. However, structural modifications at the η6‐bound arene have had significant synthetic limitations, particularly in the design of Os(II)‐tethered complexes. For the first time, we have employed a practical C(sp3)‐C(sp2) coupling to obtain 28 new Ru(II) and Os(II) η6‐arene half‐sandwich complexes with a wide variety of arene functionalities, including those that enable the formation of tether rings, such as quinoline, and coumarin. The introduction of novel functional groups at the arene in Ru(II)‐ and Os(II) half‐sandwich complexes can broaden the synthetic scope of this type of organometallic complexes, and help to take full advantage of their structural diversity, for example, in intracellular catalysis. [ABSTRACT FROM AUTHOR]

A new bidentate bridging ligand, bis(2-pyridyl)thieno[3,4-b]pyrazine is reported, along with its mono- and bi-metallic Ru(II) complexes as representative examples. Spectroscopic, electrochemical and X-ray crystallographic characterization of these species is reported, with the separation of the two Ru(III)/Ru(II) couples of the bimetallic complex suggesting better metal–metal communication than classical polypyridyl analogues. [ABSTRACT FROM AUTHOR]

Structural engineering, coupled with crystalline phase engineering and surface engineering, serves as a practical and effective strategy for enhancing catalytic performance through the fine design of catalysts in terms of their structure, physical phases and surface defects. In this work, a set of strategies were employed for structural transformation and crystalline phase transition of Ru/TiO2 catalysts, utilizing multidimensional regulation. Ru nanoparticles loaded on a unique TiO2 nanosheet flowers (Ru/TSFs) enriched with pores and Ti3+ defects were prepared by solvothermal and impregnation‐chemical reduction methods. The Ru/TSFs exhibited an outstanding catalytic performance in the reaction of selective hydrogenation of benzene for the preparation of cyclohexene, with a selectivity of 79 % and a maximum yield of 52.8 % along with a benzene conversion of 45.9 % and a good stability. The excellent catalytic performance attributes to the distinctive structure of three‐dimensional nanosheet flowers, which offers a high specific surface area and improvs the effective contact between the catalyst and the reaction substrate. Meanwhile, the porous Ru/TSFs exhibit exceptional hydrophilicity and abundant Ti3+ defects on their surface, which is quite favorable for the desorption of cyclohexene from the reaction system, thus improving the selectivity of cyclohexene. The multidimensional engineering may provide an efficient approach for constructing high‐performance loaded catalysts for potential industrial applications. [ABSTRACT FROM AUTHOR]

ABSTRACT A series of N,N‐chelate half‐sandwich ruthenium complexes based on N‐phenylpicolinamide ligands has been prepared with good yields through a facile route. These air and moisture stable N,N‐chelate half‐sandwich ruthenium complexes showed good catalytic efficiency in transamidation reactions between aromatic amines and amides under mild reaction conditions. A variety of secondary amides was obtained in high yields under open flask condition with broad substrates and good group tolerance. The excellent catalytic activity, broad substrate range, and mild reaction conditions make this catalytic system a potential candidate for industrial production. In addition, the structure of the prepared ruthenium complex has been confirmed by single crystal X‐ray diffraction. [ABSTRACT FROM AUTHOR]

Developing effective electrocatalysts for the nitrate reduction reaction (NO3RR) is a promising alternative to conventional industrial ammonia (NH3) synthesis. Herein, starting from a flexible laser‐induced graphene (LIG) film with hierarchical and interconnected macroporous architecture, a binder‐free and free‐standing Ru‐modified LIG electrode (Ru‐LIG) is fabricated for electrocatalytic NO3RR via a facile electrodeposition method. The relationship between the laser‐scribing parameters and the NO3RR performance of Ru‐LIG electrodes is studied in‐depth. At −0.59 VRHE, the Ru‐LIG electrode exhibited the optimal and stable NO3RR performance (NH3 yield rate of 655.9 µg cm−2 h−1 with NH3 Faradaic efficiency of up to 93.7%) under a laser defocus setting of +2 mm and an applied laser power of 4.8 W, outperforming most of the reported NO3RR electrodes operated under similar conditions. The optimized laser‐scribing parameters promoted the surface properties of LIG with increased graphitization degree and decreased charge‐transfer resistance, leading to synergistically improved Ru electrodeposition with more exposed NO3RR active sites. This work not only provides a new insight to enhance the electrocatalytic NO3RR performance of LIG‐based electrodes via the coordination with metal electrocatalysts as well as identification of the critical laser‐scribing parameters but also will inspire the rational design of future advanced laser‐induced electrocatalysts for NO3RR. [ABSTRACT FROM AUTHOR]

The productions of hydrogen peroxide (H2O2) and hydrogen (H2) in a photoelectrochemical (PEC) water splitting cell suffer from an onset potential that limits solar conversion efficiencies. Moreover, the formation of H2O2 through two‐electron PEC water oxidation reaction competes with four‐electron oxidation evolution reaction. Herein, we developed the surface selenium doped antimony trisulfide photoelectrode with the integrated ruthenium cocatalyst (Ru/Sb2(S,Se)3) to achieve the low onset potential and high Faraday efficiency (FE) for selective H2O2 production. The photoanode exhibits an outstanding average FE of 85 % in the potential range of 0.4–1.6 VRHE and the H2O2 yield of 1.01 μmol cm−2 min−1 at 1.6 VRHE, especially at low potentials of 0.1–0.55 VRHE with 80.4 % FE. Impressively, an unassisted PEC system that employs light and electrolyte was constructed to simultaneously produce H2O2 and H2 production on both the Ru/Sb2(S,Se)3 photoanode and the Pt/TiO2/Sb2S3 photocathode. The integrated system enables the average PEC H2O2 production rate of 0.637 μmol cm−2 min−1 without applying any addition bias. To our knowledge, this is the first demonstration that Sb2S3‐based photoelectrodes exhibit H2O2/H2 two‐side production with a strict key factor of the system, which represents its powerful platform to achieve high efficiency and productivity and the feasibility to facilitate value‐added products in neutral conditions. [ABSTRACT FROM AUTHOR]

Methods for producing drugs directly at the cancer site, particularly using bioorthogonal metal catalysts, are being explored to mitigate the side effects of therapy. Albumin‐based artificial metalloenzymes (ArMs) catalyze reactions in living mice while protecting the catalyst in the hydrophobic pocket. Here, we describe the in situ preparation and application of biocompatible tumor‐targeting ArMs using circulating albumin, which is abundant in the bloodstream. The ArM was formed using blood albumin through the intravenous injection of ruthenium conjugated with an albumin‐binding ligand; the tumor‐targeting unit was conjugated to the ArM using its catalytic activity, and the ArM was transported to the cancer site. The delivered ArM catalyzed a second tagging reaction of the proapoptotic peptide on the cancer surface, successfully suppressing cancer proliferation. This approach, which efficiently leveraged the persisting reactivity twice in vivo, holds promise for future in vivo metal‐catalyzed drug synthesis utilizing endogenous albumin. [ABSTRACT FROM AUTHOR]

Development of heterogeneous catalyst is significant key for achieving high performance of NaBH 4 hydrolysis to produce hydrogen. The stability of sodium borohydride in the presence of suitable catalyst is the efficient method to generate hydrogen. In this work, styrene-imid PIILP, polymer 1 decorated styrene, imidazolium ionic liquid, and cross-coupling is successfully synthesised by AIBN initiated radical polymerisation, then precipitation with 3,3′,3″phosphinetriyltribenzene sulfonate with ratio (1:0.3) to isolate the first styrene-imid- sulphonated PIILP, polymer 2. RuNP@styrene-imid-sulphonated PIILP, RuNPs catalyst 3 was synthesised by impregnation with RuCl 3 , then reduction by NaBH 4. Moreover, several analytical techniques such as, 31P, 1H, 13C solid-state NMR, CHN, IR, XPS, TEM, TGA-DTA, and SEM were examined to explore the obtained catalyst 3. The hydrogen generation from NaBH 4 utilizing catalyst 3 was exhibited the catalytic behaviour studying several parameters such as, temperature, catalytic loading, and NaBH 4 concentrations this work was deducted the activation energy (30.32 kJmol-1), and the turnover frequency (TOF) reached up 134.9, 112.77, and 98.38 moleH 2.mol cat −1.min−1 at 40, 35 and 30 °C. The effectiveness of Ruthenium nanoparticle catalyst 3 for the hydrolysis reaction of NaBH 4 was examined in H 2 O and D 2 O resulting kinetic isotope effect (KIE) k H /k D = 3. In addition, RuNPs demonstrated a promising efficient for reuse catalyst 3 after five cycles for the catalytic hydrolysis. [Display omitted] • RuNPs was synthesised and characterised by 31P and 13C Solid-State NMR, CHN, XPS, TEM, SEM, TGA and FT-IR. • A TOF 134.9 mole H2.mol cat −1.min−1 for RuNPs@styrene-imid-sulphonated PIILP was achieved. • E a of 30.32 for RuNPs@styrene-imid-sulphonated PIILP were achieved. • RuNPs demonstrated a promising efficiency for reuse RuNPs after five cycles for the catalytic hydrolysis. [ABSTRACT FROM AUTHOR]

5‐Hydroxymethylfurfural (HMF) is a versatile platform molecule that can be derived from biomass feedstocks and catalytically converted into various value‐added chemicals. In this work, selective hydrogenation of HMF is investigated to produce valuable furan‐based diols, namely 2,5‐bis‐hydroxymethylfuran (BHMF) and 2,5‐bis‐hydroxymethyltetrahydrofuran (BHMTHF), using TiO2 supported Ru catalysts. The catalyst performance was fine‐tuned to achieve over 98% yield to BHMF and BHMTHF under optimized reaction conditions with very good recyclability. We pointed out several key factors allowing to maximize the yield towards the respective diols. Features such as the Ru nanoparticle size, the strength of metal‐support interactions and the presence of residual chlorine were found to significantly influence the reaction. A characteristic volcano‐shaped relationship was obtained between the particle size and the catalytic activity giving the highest diol yield for an optimum Ru nanoparticle size of 1.6 nm. Further, metal‐support interactions were found to be responsible for providing optimum Ru‐TiOx interfacial surface sites and chlorine was affecting the electronic properties of Ru nanoparticles, potentially benefiting to the selective formation of BHMF. The reaction time was shown to control the hydrogenation of the furan ring and the selectivity of the reaction, that can be directed optimally towards BHMF or BHMTHF. [ABSTRACT FROM AUTHOR]

Computational aspects of concerted [2+2] oxidative‐retrocycloaddition‐cycloreversion reaction through ruthenium alkylidene π‐complexes and ruthenacyclobutane with α,β‐(C—C—C) agostic bonding interactions in olefin metathesis are presented. d6‐Ruthenium carbene complexes, with ruthenium in the oxidation state +2, undergo successive [2+2] cycloaddition and cycloreversion steps, through associative, dissociative, or interchange mechanisms. This process involves coordination of the olefin to 16‐electron Ru complex followed by phosphine dissociation, or first phosphine dissociation then coordination of the olefin to the 14‐electron Ru complex with rearrangement to a ruthenacyclobutane intermediate, followed by symmetrical reverse steps. Donation of σ‐electron density from the two C—C σ‐bonds to the metal center leads to α,β‐(C—C—C) agostic bonds, which stabilized metallacyclobutane as a formally 16‐electron complex, with lower energy than the corresponding π‐complex. In the transformation from π‐complex to ruthenacyclobutane the ruthenium atom is formally oxidized to Ru(IV). The most efficient ligands are those that stabilize the high‐oxidation state metallacyclobutane (IV) intermediate relative to the ruthenium carbene. [ABSTRACT FROM AUTHOR]

ABSTRACT Phenothiazine and thioindigo were used as substitutes to make new Ru dyes for DSSCs. The thioindigo unit is a notable molecule with strong technical qualities in these photosensitizers. As a result, research was done on the cyano substituent as an electron‐donating group. Both theoretical and experimental methods were used to assess the complexes' optical response. A better photovoltaic response is achieved by the cyano groups' efficient bonding with the semiconductor layer. Additionally, the complexes that were formed contain two different kinds of electron accepter substituents: cyanoacrylic acid and carboxylic acid, with efficiencies of 7.42% and 4.17%, respectively. Additionally, cosensitization was investigated and analyzed utilizing N719 and two generated complexes. DSSCs made with Complex 1 and 2 and N719 have corresponding efficiency percentages of 8.86% and 9.74%. [ABSTRACT FROM AUTHOR]

The B, N co-doped carbon matrix loaded with ultra-small Ru nanoparticles (Ru/BNC) is an excellent bifunctional catalyst capable of efficiently catalyzing ammonia borane hydrolysis and alkaline water electrolysis for hydrogen evolution. [Display omitted] Developing a straightforward and general strategy to regulate the surface microenvironment of a carbon matrix enriched with N/B motifs for efficient atomic utilization and electronic state of metal sites in bifunctional hydrogen production via ammonia-borane hydrolysis (ABH) and water electrolysis is a persistent challenge. Herein, we present a simple, green, and universal approach to fabricate B/N co-doped porous carbons using ammonia-borane (AB) as a triple functional agent, eliminating the need for hazardous and explosive functional agents and complicated procedures. The pyrolysis of AB induces the regulation of the surface microenvironment of the carbon matrix, leading to the formation of abundant surface functional groups, defects, and pore structures. This regulation enhances the efficiency of atom utilization and the electronic state of the active component, resulting in improved bifunctional hydrogen evolution. Among the catalysts, B/N co-doped vulcan carbon (Ru/BNC) with 2.1 wt% Ru loading demonstrates the highest performance in catalytic hydrogen production from ABH, achieving an ultrahigh turnover frequency of 1854 min−1 (depending on the dispersion of Ru). Furthermore, this catalyst shows remarkable electrochemical activity for hydrogen evolution in alkaline water electrolysis with a low overpotential of 31 mV at 10 mA cm−2. The present study provides a simple, green, and universal method to regulate the surface microenvironment of various carbons with B/N modulators, thereby adjusting the atomic utilization and electronic state of active metals for enhanced bifunctional hydrogen evolution. [ABSTRACT FROM AUTHOR]

Ruthenium‐indane complex, fac‐[Ru(NCMe)3(CO)2(InCl3)] 1Cl reacted with 0.5 equiv. of dppe/dppp to afford dinuclear ruthenium‐indane complexes linked by diphosphine ligand, [{Ru(NCMe)2(CO)2(InCl3)}2{μ2‐Ph2P(CH2)nPPh2}] (n=2: 3, 3: 4). On the other hand, the reaction of fac‐[Ru(NCMe)3(CO)2(InCl3)] 1Cl with 1 equiv. of dppp afforded the corresponding chelate ruthenium(0) indane complex, [Ru(NCMe)(CO)2(InCl3)(dppp)] 5. In the case of dppm, a chelate complex [Ru(NCMe)(CO)2(InCl3)(dppm)] 6 was formed via the dinuclear Ru complex [{Ru(NCMe)2(CO)2(InCl3)}2(μ2‐dppm)]. Complexes 1Cl, 5, and 6 showed a catalytic activity for double‐hydrosilylation of MeCN. Complexes 3–6 were fully characterized using NMR measurements, elemental analyses, and the structures of 1Cl, 3, 5, and 6 were determined by X‐ray crystallography. [ABSTRACT FROM AUTHOR]

The catalytic hydrogenation of CO2 to formate was achieved using the previously reported dichloro(η6‐p‐cymene){diphenyl(3‐methyl‐2‐indolyl)phosphine}ruthenium (1) as a catalyst under mild conditions. In this complex, the phosphorus‐based ligand adopts a κ1‐P coordination mode. The catalytic activity was achieved in the presence of DBU as a base providing a TONmax value of 3,800. In order to explore potential transformations occurring within the catalytic reactions, a series of stoichiometric tests were performed. Complex 1 was reacted with DBU to form chloro(η6‐p‐cymene){diphenyl(3‐methyl‐2‐indolide)phosphine}ruthenium (2). Structural characterization of complex 2 confirmed a κ2‐P,N coordination mode for the ligand resulting in a four membered metallacycle. Reaction of 2 with H2 led to the formation of hydrochloro(η6‐p‐cymene){diphenyl(3‐methyl‐indolyl)phosphine}ruthenium (3), albeit not with a clean conversion. This is the product resulting from the formal addition of hydrogen across the Ru−N bond of the metallacycle. Complex 3 was also synthesized via an alternative route involving the reaction of complex 1 with Me2NH • BH3 as a means of converting Ru−Cl to Ru−H [ABSTRACT FROM AUTHOR]

Although ruthenium dioxide (RuO2) is an efficacious oxygen evolution reaction (OER) catalyst in acidic media, its performance in alkaline conditions is subpar and it is also ineffective for hydrogen evolution reaction (HER) in common electrolytes. Here, an effective phosphorus (P)‐doping strategy is introduced to manipulate the d‐band center of ruthenium (Ru) sites, attenuating the adsorption energy of HER intermediates and lowering the energy barrier in OER, thereby significantly accelerating both HER and OER performance. The representative 10%P‐RuO2 nanofibers (NFs) catalyst presents an ultralow overpotential of 177.9 mV at 1 A cm−2 and long‐term stability of 300 h in 1 m KOH toward HER, greatly exceeding those of benchmark platinum (Pt)/C catalyst. Moreover, the 10%P‐RuO2 NFs catalyst exhibits an exceptional OER performance with a low overpotential of 250 mV at 10 mA cm−2 (η10) and desirable stability of 150 h at 1 A cm−2, which is far better than commercial RuO2 and many other typical previously reported OER catalysts. Additionally, an overall water electrolytic cell using 10%P‐RuO2 NFs as both anode and cathode necessitates a working voltage of 1.52 V (η10) and demonstrates long‐term stability over 100 h at 1 A cm−2, outperforming many typical water electrolysis cells. [ABSTRACT FROM AUTHOR]

Selective hydrogenation of carboxylic acids to alcohols is generally difficult due to the low reactivity of the carboxy group, and the development of effective catalysts enabling high yields of the target alcohols at low reaction temperatures (<473 K) is challenging. Herein, we found that SiO2‐supported FeOx‐modified Ru (Ru−FeOx/SiO2) with the Fe/Ru molar ratio of 0.4 was an effective and reusable heterogeneous catalyst for the hydrogenation of carboxylic acids at a low reaction temperature of 413 K, providing the alcohols in high yields (up to 97 %). The addition of Fe species drastically suppressed the hydrogenolysis of the C−C bond of the alkyl chain to methane, leading to high selectivity to the alcohols. Based on the activity tests and catalyst characterizations, Ru metals were covered by the reduced Fe species, such as Fe metal or Fe2+, and the active site is the interface between the Fe species and Ru metals. From the reactivity comparison of the related compounds, the alcohol is synthesized via the formation of the aldehyde, and the reactivity of the alcohol is very low in the presence of carboxylic acids. As a result, the hydrogenolysis of the produced alcohol is suppressed, leading to the high selectivity of the alcohol. [ABSTRACT FROM AUTHOR]

The synthesis and isolation of [Ru(Cp)(PCy2NPh2)(=C=CHPh]PF6 and [Ru(Cp*)(PCy2NCy2)(=C=CHPh)]PF6 was successfully accomplished. Use of these ruthenium vinylidene complexes for stoichiometric reactions with a variety of amines was performed. Upon reaction with alkyl amines, deprotonation of the Cβ hydrogen resulted in formation of acetylide complex [Ru(Cp*)(PCy2NPh2)(−C≡CPh)], and the species was confirmed through independent synthesis. In contrast, reaction of the less basic aryl amine aniline with [Ru(Cp)(PCy2NCy2)(=C=CHPh)]PF6 resulted in outer sphere addition to give a Fischer carbene product. [ABSTRACT FROM AUTHOR]

A first example of a mitochondrial G‐quadruplex (mitoG4s) targeted Ru(II) photooxidant complex is reported. The complex, Ru‐TAP‐PDC3 induces photodamage toward guanine quadruplexes (G4s) located in the mitochondrial genome under hypoxic and normoxic conditions. Ru‐TAP‐PDC3 shows high affinity for mitoG4s and localises within mitochondria of live HeLa cells. Immunolabelling with anti‐G4 antibody, BG4, confirms Ru‐TAP‐PDC3 associates with G4s within the mitochondria of fixed cells. The complex induces depletion of mtDNA in live cells under irradiation at 405 nm, confirmed by loss of PicoGreen signal from mitochondria. Biochemical studies confirm this process induces apoptosis. The complex shows low dark toxicity and an impressive phototoxicity index (PI) of >89 was determined in Hela under very low intensity irradiation, 5 J/cm2. The phototoxicity is thought to operate through both Type II singlet oxygen and Type III pathways depending on normoxic or hypoxic conditions, from live cell assays and plasmid DNA cleavage. Overall, we demonstrate targeting mitoG4s and mtDNA with a photooxidant is a potent route to achieving apoptosis under hypoxic conditions that can be extended to phototherapy. [ABSTRACT FROM AUTHOR]

It has been known that plastics with undegradability and long half‐times have caused serious environmental and ecological issues. Considering the devastating effects, the development of efficient plastic upcycling technologies with low energy consumption is absolutely imperative. Catalytic hydrogenolysis of single‐use polyethylene over Ru‐based catalysts to produce high‐quality liquid fuel has been one of the current top priority strategies, but it is restricted by some tough challenges, such as the tendency towards methanation resulting from terminal C−C cleavage. Herein, we introduced Ru nanoparticles supported on hollow ZSM‐5 zeolite (Ru/H‐ZSM‐5) for hydrocracking of high‐density polyethylene (HDPE) under mild reaction conditions. The implication of experimental results is that the 1Ru/H‐ZSM‐5 (~1 wt % Ru) acted as an effective and reusable bifunctional catalyst providing higher conversion rate (82.53 %) and liquid fuel (C5−C21) yield (62.87 %). Detailed characterization demonstrated that the optimal performance in hydrocracking of PE could be attributed to the moderate acidity and appropriate positively charged Ru species resulting from the metal‐zeolite interaction. This work proposes a promising catalyst for plastic upcycling and reveals its structure‐performance relationship, which has guiding significance for catalyst design to improve the yield of high‐value liquid fuels. [ABSTRACT FROM AUTHOR]

Biomass valorisation through the selective oxidation of carbohydrate and lipid derivatives offers access to an array of platform chemicals through energy- and atom-efficient catalytic processes. Supported metal nanoparticles are promising catalysts for the aerobic selective oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA), but typically require strong liquid base to achieve high selectivity. Here, we explore the utility of MgO as a solid base support for the Ru-catalysed aerobic oxidation of HMF, obtaining 68% FDCA yield at 160°C and 1.5 MPa of O2 using <1 mol-% metal. Biomass offers a sustainable alternative source of carbon to existing fossil resources that underpin the global chemical industry – on which we rely for fuels, plastics and pharmaceuticals. Combining ruthenium metal with Earth-abundant magnesium oxide creates an efficient catalyst for transforming sugar components of waste biomass into a valuable precursor for the sustainable manufacture of plastics. (Image credit: Priya Lokhande.) This article belongs to the 10th Anniversary Collection of RACI and AAS Award papers. [ABSTRACT FROM AUTHOR]

Rh(III) and Ru(II) complexes, [RhCl2(κ4‐N2N'P‐L)][SbF6] (1) and [RuCl2(κ4‐N2N'P‐L)] (2), were synthesised using the tetradentate ligand L (L=N,N‐bis[(pyridin‐2‐yl)methyl]‐[2‐(diphenylphosphino)phenyl]methanamine). In each case only one diastereomer is detected, featuring cis‐disposed pyridine groups. The chloride ligand trans to pyridine can be selectively abstracted by AgSbF6, with the ruthenium complex (2) reacting more readily at room temperature compared to the rhodium complex (1) which requires elevated temperatures. Rhodium complexes avoid the second chloride abstraction, whereas ruthenium complexes can form the chiral bisacetonitrile complex [Ru(κ4‐N2N'P‐L)(NCMe)2][SbF6]2 (5) upon corresponding treatment with AgSbF6. The complex [RhCl2(κ4‐N2N'P‐L)][SbF6] (1) has also been used to synthesise polymetallic species, such as the tetrametallic complex [{RhCl2(κ4‐N2N'P‐L)}2(μ‐Ag)2][SbF6]4 (6) which was formed with complete diastereoselectivity and chiral molecular self‐recognition. In addition, a stable bimetallic mixed‐valence complex [{Rh(κ4‐N2N'P‐L)}{Rh(COD)}(μ‐Cl)2][SbF6]2 (7) (COD=cyclooctadiene) was synthesised. These results highlight the significant differences in chloride lability between Rh3+ and Ru2+ complexes and demonstrate the potential for complexes to act as catalyst precursors and ligands in further chemistry applications. [ABSTRACT FROM AUTHOR]

Ruthenium quantities in borosilicate glasses, used in vitrification process to nuclear waste immobilization, is uncertain due to the volatility of ruthenium oxide. In this work, a quantitative method was developed to determinate the content of ruthenium in the borosilicate glasses containing nuclear waste tracer nuclides by inductively coupled plasma mass spectrometry (ICP-MS). The research showed that the ruthenium in borosilicate glasses can be completely decomposed by NaOH at 350 °C for 8 h. A recovery of no less than 95% and a detection limit of 0.4 mg kg−1 were obtained. The method has been successfully applied for the determination of actual samples. [ABSTRACT FROM AUTHOR]

The need for abundant, sustainable, and clean energy is becoming increasingly important in the modern world due to continuous population growth and industrial expansion. Hydrogen (H2) has been identified as a potential energy carrier due to its high gravimetric energy density. Because H2 is not frequently found in its molecular form, it has to be obtained through various methods such as steam methane reforming, coal gasification, fossil fuels, and electrochemical techniques. H2 produced via PEMWE has proved to be an efficient method compared to other electrolysers. The limiting factor of a PEM electrolyser system is the OER catalyst. Commercially, IrO2 and RuO2 are used; however, both these metals are rare and expensive. Current research reports the use of binary metal oxides as an alternative OER catalyst to decrease the overall CAPEX costs. Various synthesis methods are available, with the Adams' fusion method being the simplest. Characterisation techniques used to evaluate the performance of these catalysts include cyclic voltammetry (CV), linear scan voltammetry (LSV), XRD, XRF, SEM/EDS, and chronopotentiometry. Hydrogen as a clean fuel has a broad potential for use across all sectors, including transportation, residential, and industrial. In recent years, extensive research has been done on all aspects of hydrogen production, storage, and transportation. This review paper aims to study other bimetallic metals to reduce the Ir content used as an oxidative evolution reaction to reduce the capital cost of the PEM electrolyser. To produce green hydrogen that could reduce the carbon footprint in several industrial processes. [ABSTRACT FROM AUTHOR]

Active and robust electrocatalysts for acidic oxygen evolution reaction (OER) are of crucial importance for efficient proton exchange membrane water electrolyzer (PEM‐WE). Ruthenium (Ru) oxide has attracted considerable attention due to its high activity. However, the unsatisfying stability of Ru oxide in acidic OER environments hinders the application. Here, Ce‐doped RuO2 nanoparticles are designed and supported on Co─N─C material (Ce@RuO2/CoNC) for acidic OER. It is demonstrated that Ce@RuO2/CoNC delivers a super low overpotential of 150 mV and an excellent stability of 1000 h at 10 mA cm−2, outperforming most previously reported Ru‐based catalysts. The mass activity is estimated as 2365.5 AgRu−1 at 1.5 V (vs RHE), representing ≈2× advance compared to the best prior study. Furthermore, applied in a single‐cell PEM‐WE device, it can steadily operate for 1000 h at 200 mA cm−2. The studies show that Ce‐doping and Co─N─C support synergistically enhance the activity and stability of Ru oxide by optimizing the free energies of OER intermediates and suppressing the dissolution of Ru. [ABSTRACT FROM AUTHOR]

The activity profile of the new indenylidene complexes containing two unsymmetrical N‐heterocyclic carbene (NHC) ligands was investigated. They turned out to be effective in both straightforward olefin metathesis reactions, such as ring‐closing metathesis (RCM) of diethyl diallylmalonate, as well as in more demanding processes, such as RCM of 2,2‐di‐(2‐methylallyl)tosylate leading to a product bearing a tetrasubstituted double bond, and in selective ethenolysis of methyl and ethyl oleate. [ABSTRACT FROM AUTHOR]

The application of cationic Ru(II)‐CNC pincer complexes [Ru(CNC)(CO)(PPh3)Cl]PF6 (1), [Ru(CNC)(PPh3)2Cl]PF6 (2), [Ru(CNC)(η2:η2‐COD)Cl]PF6 (4), and [Ru(CNC)(DMSO)2Cl]PF6 (5) in acceptorless dehydrogenation of alcohols is reported under conventional "oil‐bath" and microwave heating conditions. The effect of different ancillary ligands (CO, PPh3, COD, and DMSO) have been demonstrated during catalysis. Complexes with more π‐acid ligands CO and COD perform better compared with those with PPh3 and DMSO ligands. A plausible mechanism is proposed based on NMR and mass investigation during the catalysis. The catalytic performance matches with the order of trans effect among the four ancillary ligands studied in these complexes. Further, a significant reduction in reaction time, as well as reaction temperature, was observed for catalytic reactions under the microwave‐assisted reaction compared with the oil‐bath heating reaction. [ABSTRACT FROM AUTHOR]

A new approach for the preparation of a variety of 3-arylated 2-furoic acid derivatives has been developed. The approach involves selective Ru-catalyzed C3-H arylation of the furan moiety of readily available 2-furoyl-1-methylimidazole (using imidazole as a removable N-donor directing group), subsequent N-methylation, and nucleophilic substitution of the imidazole moiety with N, O, S, and C nucleophiles. [ABSTRACT FROM AUTHOR]

Controlling the electronic structure based on the valence state is key for effective electrocatalysis, and the challenge lies in attaining the optimal metal valence states. Here, a new approach called valence‐elastic control is introduced to create intermediate‐valence Ru species within a‐RuOx/C catalyst matrices. By utilizing hetero‐interfaces between RuOx and C, pathways for efficient electron transfer and precise valence adjustment are activated through switchable bonding at the interfaces. The catalyst demonstrates exceptional performance in hydrogen evolution reaction with an unprecedentedly low overpotential of 4.1 mV in KOH + seawater electrolytes at 10 mA cm−2. Furthermore, the two‐electrode electrolyzer demonstrates improved stability and voltage efficiency compared to the commercial Pt/C‐based system. The in situ tests combined with theoretical analysis reveal the water dissociation and *H adsorption are optimized by the switchable interface bonding of the tailored Ru species. This study showcases a transformative design framework for next‐generation high‐efficiency metal catalysts with variable valence. [ABSTRACT FROM AUTHOR]

Chromophore–catalyst assemblies are interesting benchmark molecules for photocatalysis. We have prepared two examples of these assemblies and characterized their behaviour as catalysts for the water oxidation reaction. In the bimetallic complexes [Ru(tpy)(4,4′-X2-bpy)(μ-CN)Ru(bda)(DMSO)](PF6) (X = –H (1), –OCH3 (2), tpy = 2,2′:6′,2′′-terpyridine, bpy = 2,2′-bipyridine, H2bda = 2,2′-bipyridine-6,6′-dicarboxylic acid and DMSO = (CH3)2SO), a Ru(II)-polypiridine chromophore {Ru(tpy)(4,4′-X2-bpy)} is linked by a cyanide bridge to a {Ru(bda)} water oxidation catalyst. Both complexes catalyze water oxidation both chemically, using Ce(IV) as the terminal oxidant, and electrochemically. Electrochemical and spectroelectrochemical studies, aided with (TD)DFT calculations, allowed us to study the different species involved in the catalytic cycle. For the RuIIRuIII, an intense MMCT (metal-to-metal charge transfer) band suggests a geometrical reorganization during the oxidation process. The wave associated with oxidation to the RuIIIRuIV species shows an increased current that suggests that it may be a catalyst for the water oxidation reaction. Further oxidation results in the RuIIIRuV redox state which is an active catalyst for the water oxidation reaction as demonstrated by the evolution of oxygen. [ABSTRACT FROM AUTHOR]

Because of its current and future intensive use, the synthesis of sustainable ammonia is of major concern. This study focuses on highlighting the mechanistic behaviours of NH3 production from molecular nitrogen and hydrogen on ruthenium materials supported on cerium‐based ternary intermetallics. An interesting activity is reported for Ru/CeTX materials (T=Sc, Ti; X=Si, Ge) with an ammonia production rate around 0.60 mmolNH3 h−1 g−1 at only 300 °C and 1 bar. While the activity at 400 °C appeared attributable to the N≡N cleavage activation, this low‐temperature activity is no longer correlated with this parameter, but rather to the behaviour regarding hydrogen and especially the ability of cerium‐based intermetallic materials to desorb hydrogen from the structure, supporting an associative‐type mechanism. [ABSTRACT FROM AUTHOR]

The hydrogenolysis of polymers is emerging as a promising approach to deconstruct plastic waste into valuable chemicals. Yet, the complexity of plastic waste, including multilayer packaging, is a significant barrier to handling realistic waste streams. Herein, we reveal fundamental insights into a new chemical route for transforming a previously unaddressed fraction of plastic waste – poly(ethylene‐co‐vinyl alcohol) (EVOH) and related polymer blends – into alkane products. We report that Ru/ZrO2 is active for the concurrent hydrogenolysis, hydrogenation, and hydrodeoxygenation of EVOH and its thermal degradation products into alkanes (C1−C35) and water. Detailed reaction data, product analysis, and catalyst characterization reveal that the in‐situ thermal degradation of EVOH forms aromatic intermediates that are detrimental to catalytic activity. Increased hydrogen pressure promotes hydrogenation of these aromatics, preventing catalyst deactivation and improving alkane product yields. Calculated apparent rates of C−C scission reveal that the hydrogenolysis of EVOH is slower than low‐density polyethylene. We apply these findings to achieve hydrogenolysis of EVOH/polyethylene blends and elucidate the sensitivity of hydrogenolysis catalysts to such blends. Overall, we demonstrate progress towards efficient catalytic processes for the hydroconversion of waste multilayer film plastic packaging into valuable products. [ABSTRACT FROM AUTHOR]

A novel methodology for the synthesis of 2-pyridones bearing a 2-pyridyl group on nitrogen and carbon atoms, starting from 2-bromopyridines, was developed employing a simple Ru(II)–KOPiv–Na2CO3 catalytic system. Unsubstituted 2-bromopyridine was successfully converted to the penta-heteroarylated 2-pyridone product using this method. Preliminary mechanistic studies revealed a possible synthetic pathway leading to the multi-heteroarylated 2-pyridone products, involving consecutive oxygen incorporation, a Buchwald–Hartwig-type reaction, and C–H bond activation. [ABSTRACT FROM AUTHOR]

Four new complexes [Ru(bpy)2(bbib)](PF6)2, [Ru(phen)2(bbib)](PF6)2, [Re(CO)3(bbib)(py)](PF6) and [Ir(ppy)2(bbib)](PF6) [where bbib=4,4′‐bis(benzimidazol‐2‐yl)‐2,2′‐bipyridine] have been prepared and their photophysical properties determined. Their behaviour has been studied with a variety of anions in acetonitrile, DMSO and 10 % aquated DMSO. Acetate and dihydrogenphosphate demonstrate a redshift in the bbib ligand associated absorptions suggesting that the ligand is strongly interacting with these anions. The 3MLCT emissive state is sensitive to the introduction of small quantities of anion (sub‐stoichiometric quantities) and significant quenching is typically observed with acetate, although this is less pronounced in the presence of water. The emissive behaviour with dihydrogenphosphate is variable, showing systematic changes as anion concentration increases with several distinct interactions evident. 1H‐ and 31P‐NMR titrations in a 10 % D2O−DMSO‐D6 mixture suggest that with dihydrogenphosphate, the imidazole group is able to act as both a proton acceptor and donor. It appears that all four complexes can form a {[complex]2‐H2PO4} "dimer", a one‐to‐one species (which the X‐ray crystallography study suggests is dimeric in the solid‐state), and a complex with a combined bis(dihydrogenphosphate) complex anion. The speciation relies on complex equilibria dependent on several factors including the complex charge, the hydrophobicity of the associated ligands, and the solvent. [ABSTRACT FROM AUTHOR]

Colloidal metal nanoparticles exhibit interesting catalytic properties for the hydrogenation of (hetero)arenes. Catalysts based on precious metals, such as Ru and Rh, promote this reaction efficiently under mild reaction conditions. In contrast, heterogeneous catalysts based on earth‐abundant metals can selectively hydrogenate (hetero)arenes but require harsher reaction conditions. Bimetallic catalysts that combine precious and earth‐abundant metals are interesting materials to mitigate the drawbacks of each component. To this end, RuNi nanoparticles bearing a phosphine ligand were prepared through the decomposition of [Ru(η4‐C8H12)(η6‐C8H10)] and [Ni(η4‐C8H12)2] by H2 at 85 °C. Wide angle X‐ray scattering confirmed a bimetallic segregated structure, with Ni predominantly on the surface. Spectroscopic analyses revealed that the phosphine ligand coordinated to the surface of both metals, suggesting, as well, a partial Ni shell covering the Ru core. The RuNi‐based nanomaterials were used as catalysts in the hydrogenation of quinoline to assess the impact of the metallic composition and of the stabilizing agent on their catalytic performance. [ABSTRACT FROM AUTHOR]

This research focused on the synthesis and analysis of two novel Ru(II)-based complexes, cis-[RuCl(Hind)(phen)2]PF6 (FOR022) and cis-[Ru(Hind)2(phen)2](PF6)2 (FOR0E2), where Hind represents indazole and phen stands for 1,10-phenanthroline. These compounds were thoroughly characterized using various methods such as elemental analysis, spectroscopy techniques, and electrochemistry assay, confirming their structures. The research highlights the effectiveness of the compound FOR0E2 in exhibiting strong cytotoxic properties against various tumor cell lines, including HCT116, HepG2, HL-60, LNcaP, and PC-3, with half-maximal inhibitory concentration (IC50) values ranging from 10.7 to 25.2 μmol L−1. Additionally, FOR0E2 showed substantial leishmanicidal capabilities against both the promastigote and amastigote forms of L. amazonensis, with IC50 values of 5.7 μmol L−1 and 1.6 μmol L−1, respectively. These outcomes suggest that the inclusion of indazole in FOR022 and FOR0E2 significantly enhances their biological effectiveness, positioning it as a promising candidate for pharmacological treatments. [ABSTRACT FROM AUTHOR]

Staphylococcus aureus (S. aureus) infection is a primary cause of otitis media (OM), the most common disease for which children are prescribed antibiotics. However, the abuse of antibiotics has led to a global increase in antimicrobial resistance (AMR). Nanozymes, as promising alternatives to traditional antibiotics, are being extensively utilized to combat AMR. Here, we synthesize a series of single-atom nanozymes (metal-C3N4 SANzymes) by loading four metals (Ag, Fe, Cu, Ru) with antibacterial properties onto a crystalline g-C3N4. These metal-C3N4 display a rob-like morphology and well-dispersed metal atoms. Among them, Ru-C3N4 demonstrates the optimal peroxidase-like activity (285.3 U mg-1), comparable to that of horseradish peroxidase (267.7 U mg-1). In vitro antibacterial assays reveal that Ru-C3N4 significantly inhibits S. aureus growth compared with other metal-C3N4 even at a low concentration (0.06 mg mL-1). Notably, Ru-C3N4 acts as a narrow-spectrum nanoantibiotic with relative specificity against Gram-positive bacteria. Biofilms formed by S. aureus are easily degraded by Ru-C3N4 due to its high peroxidase-like activity. In vivo, Ru-C3N4 effectively eliminates S. aureus and relieves ear inflammation in OM mouse models. However, untreated OM mice eventually develop hearing impairment. Due to its low metal load, Ru-C3N4 does not exhibit significant toxicity to blood, liver, or kidney. In conclusion, this study presents a novel SANzyme-based antibiotic that can effectively eliminate S. aureus and treat S. aureus-induced OM. [ABSTRACT FROM AUTHOR]

Ultrafine ruthenium nanoparticles are encapsulated by single-atom Ni-bonded graphitic carbon nitride (g-C3N4) layers anchored on carbon nanotubes (Ru/Ni-CNCT). The enhanced electronic interaction between Ru nanoparticles and Ni–N(O)–C sites anchored in g-C3N4 layers promotes water adsorption/dissociation and hydrogen evolution. [ABSTRACT FROM AUTHOR]

Bimetallic PtRu/C catalysts have been prepared by depositing Ru onto a commercial Pt/C catalyst and subsequent thermal annealing. Different Pt : Ru ratios of 1 : 1, 2 : 1, 4 : 1, 8 : 1, and 16 : 1 have been investigated with annealing temperatures of 350 and 500 °C. Using X‐ray diffraction (XRD), synchrotron powder X‐ray diffraction (SPXRD) combined with pair distribution function (PDF) analysis and scanning transmission electron microscopy with energy dispersive X‐ray spectrum imaging (STEM‐EDXS), we show that diffusion of Ru into the fcc crystal structure of the Pt nanoparticles takes place during thermal annealing. Partial segregation and the formation of Pt nanoclusters on the bimetallic surface was observed depending on the Pt : Ru ratio. The annealing process does not only cause a high Pt dispersion but also affects the electronic structure of the Pt surface by broadening the d‐band thus facilitating the product's desorption from the surface of the bimetallic particle. These beneficial effects have been exemplified for the catalytic dehydrogenation of dicyclohexylmethanol, a promising hydrogen carrier compound with 7.2 wt% hydrogen capacity. The most active catalyst material among the tested supported alloys and monometallic reference materials was Pt4Ru1/C after annealing at 500 °C, which increased the hydrogen release productivity by 65 % compared to the unmodified Pt/C catalyst. [ABSTRACT FROM AUTHOR]

A new hydroxo‐bridged ruthenium (II) complex [{Ru(η6‐p‐cymene)(iPr2P−O)}2(μ‐OH)]Cl (2) has fortuitously been isolated from the reaction between the known ruthenium(II) complex [RuCl2(η6‐p‐cymene)(iPr2P‐OH)] (1) in either CDCl3 or CHCl3 solutions in the presence of excess DBU (1,8‐diazabicyclo(5.4.0)undec‐7‐ene) at room temperature. Complex 2 is only formed under specific conditions as an orange‐colored air and moisture stable binuclear complex. It is formed via the deprotonation of the P−OH unit in [RuCl2(η6‐p‐cymene)(iPr2P‐OH)]. Complex 2 has been fully characterized by spectroscopic and analytical methods. Its structure was determined by single crystal X‐ray diffraction which reveals a boat‐shaped motif containing a bridging hydroxide unit which undergoes hydrogen bonding with a chloride counterion. Complex 2 was utilized as a catalyst for the hydrogenation of CO2 to formic acid salt using molecular hydrogen. The catalytic reactions were performed at 100 °C in THF in the presence of DBU as a base to isolate [DBU+H][OC(O)H] salt as the final product. Using catalyst loadings down to 0.01 mol%, it was possible to hydrogenate gaseous CO2 with TONs up to 9900. [ABSTRACT FROM AUTHOR]

The synthesis of amides holds great promise owing to their impeccable contributions as building blocks for highly valued functional derivatives. Herein, we disclose the design, synthesis and crystal structure of a mixed-ligand ruthenium(II) complex, [Ru(η6-Cym)(O,O-PLY)Cl], (1) where Cym = 1-isopropyl-4-methyl-benzene and O,O-PLY = deprotonated form of 9-hydroxy phenalenone (HO,O-PLY). The complex catalyzes the aerobic oxidation of various primary amines (RCH2NH2) to value-added amides (RCONH2) with excellent selectivity and efficiency under relatively mild conditions with common organic functional group tolerance. Structural, electrochemical, spectroscopic, and computational studies substantiate that the synergism between the redox-active ruthenium and π-Lewis acidic PLY moieties facilitate the catalytic oxidation of amines to amides. Additionally, the isolation and characterization of key intermediates during catalysis confirm two successive dehydrogenation steps leading to nitrile, which subsequently transform to the desired amide through hydration. The present synthetic approach is also extended to substitution-dependent tuning at PLY to tune the electronic nature of 1 and to assess substituent-mediated catalytic performance. The effect of substitution at the PLY moiety (5th position) leads to structural isomers, which were further evaluated for the catalytic transformations of amine to amides under similar reaction conditions. [ABSTRACT FROM AUTHOR]

A new hydroxo‐bridged ruthenium (II) complex [{Ru(η6‐p‐cymene)(iPr2P−O)}2(μ‐OH)]Cl (2) has fortuitously been isolated from the reaction between the known ruthenium(II) complex [RuCl2(η6‐p‐cymene)(iPr2P‐OH)] (1) in either CDCl3 or CHCl3 solutions in the presence of excess DBU (1,8‐diazabicyclo(5.4.0)undec‐7‐ene) at room temperature. Complex 2 is only formed under specific conditions as an orange‐colored air and moisture stable binuclear complex. It is formed via the deprotonation of the P−OH unit in [RuCl2(η6‐p‐cymene)(iPr2P‐OH)]. Complex 2 has been fully characterized by spectroscopic and analytical methods. Its structure was determined by single crystal X‐ray diffraction which reveals a boat‐shaped motif containing a bridging hydroxide unit which undergoes hydrogen bonding with a chloride counterion. Complex 2 was utilized as a catalyst for the hydrogenation of CO2 to formic acid salt using molecular hydrogen. The catalytic reactions were performed at 100 °C in THF in the presence of DBU as a base to isolate [DBU+H][OC(O)H] salt as the final product. Using catalyst loadings down to 0.01 mol%, it was possible to hydrogenate gaseous CO2 with TONs up to 9900. [ABSTRACT FROM AUTHOR]

Herein we demonstrate an effective and facile end‐capping technique for ring‐opening metathesis polymerization (ROMP) using readily available allyl compounds as a new type of terminating agents. This new type of end‐capping reactions, which are based on the base‐promoted decomposition of ruthenocyclobutane intermediates, introduce diene moiety onto the chain end of ROMP polymers while simultaneously deactivating the ruthenium complex. These termination reactions are highly efficient, typically completing within 1 minute at 0 °C with >95 % end‐capping fidelity. [ABSTRACT FROM AUTHOR]

Due to its abundant resources and advantages in transportation and storage, methane fueled solid oxide fuel cells (SOFCs) are highly needed. In this work, an exceptional internal reforming catalyst comprising in-situ exsolved NiRu bimetallic nanoparticles and oxygen-deficient layered double perovskite LaBaMn 1.6 Ni 0.3 Ru 0.1 O 5+δ (r-LBMNR) was prepared. Compared to the cell with LaBaMn 1.6 Ni 0.4 O 5+δ (r-LBMN) catalyst, the cell with a Ru-doping r-LBMNR catalyst layer, exhibits superior peak power output of 336 mW cm−2 and better durability with a less decay rate of 0.014% per hour in CH 4 fuel. The enhanced electrochemical performance can be attributed to the high oxygen ion and electron conductivities of the catalyst and the coupling of Ni and Ru sites with the oxygen-deficient r-LBMNR matrix This coupling activates CH 4 and H 2 O, promotes the oxidation of C atoms in CH 4 molecules, and enables reversible hydrogen spillover, ultimately leading to the production syngas of CO(g) and H 2 (g). [Display omitted] • Trace Ru-doping facilitating the exsolution of nanoparticles. • LaBaMn 1.6 Ni 0.3 Ru 0.1 O 5+δ was modified with abundant O v and exsolved NiRu alloy. • Cell can operate stably over 220 h with a degradation rate of 0.014% h−1. [ABSTRACT FROM AUTHOR]

Dicarbonyl[10,10‐dimethyl‐5,15‐bis(pentafluorophenyl)biladiene]ruthenium(II), [Ru(C33H16F10N4)(CO)2] or Ru(CO)2[DMBil1], is the first reported ruthenium(II) cis‐dicarbonyl tetrapyrrole complex. The neutral complex sports two carbonyls and an oligotetrapyrrolic biladiene ligand. Notably, the biladiene adopts a coordination geometry that is well distorted from square planar and much more closely approximates a seesaw arrangement. Accordingly, Ru(CO)2[DMBil1] is not only the first ruthenium cis‐dicarbonyl with a tetrapyrrole ligand, but also the first metal biladiene complex in which the tetrapyrrole does not adopt a (pseudo‐)square‐planar coordination geometry. Ru(CO)2[DMBil1] is weakly luminescent, displaying λem = 552 nm upon excitation at λex = 500 nm, supports two reversible 1 e− reductions at −1.45 and −1.73 V (versus Fc+/Fc), and has significant absorption features at 481 and 531 nm, suggesting suitability for photocatalytic and photosensitization applications. While the structure of Ru(CO)2[DMBil1] was initially determined by X‐ray diffraction, a traditionally acceptable quality structure could not be obtained (despite multiple attempts) because of consistently poor crystal quality. An independent structure obtained from electron diffraction experiments corroborates the structure of this unusual biladiene complex. [ABSTRACT FROM AUTHOR]

In the periodic table of the elements, ruthenium occupies an excellent position, just below iron. And like iron, it possesses several oxidation states, with +2 and +3 being the most common. Accordingly, ruthenium chemistry is extremely rich and well developed, and ruthenium complexes show excellent catalytic aptitude, tremendous redox capacity, and intriguing biological activity. However, in the design of sensors, the use of ruthenium complexes can be better exploited, as they possess valuable electro- and photochemical properties. Therefore, there is an opportunity here, and ruthenium-based complexes might become, one day, key players in sensing technology. Starting a new research project with ruthenium-based sensors ourselves, writing this review was essential to see the current state of research in the field, to better identify opportunities and to have an overview of state-of-the-art examples. [ABSTRACT FROM AUTHOR]