Ruthenium Complexes Research Articles

Catalytic Water Oxidation by Ruthenium Complexes with Pyridine Alkoxide Ligands

AbstractLigand design is crucial for the design of robust and efficient molecular water oxidation catalysts (WOCs) based on metal complexes. Herein we report the water oxidation studies of a series of Ru WOCs bearing bipyridine dialkoxide ligands with different substituents. Combined with density functional theory (DFT) calculations, the proposed water oxidation mechanism is bimolecular coupling (I2M) of two seven‐coordinate (CN7) Ru=O species. The use of bulky phenyl groups on the planar alkoxide ligand helps to stabilize the high oxidation CN7 intermediates, without loss of ligand flexibility. This strategy may be useful for the design of other active WOCs.

Dehydrogenation of Aqueous Formic Acid by Iridium and Ruthenium Complexes with Nitrogen‐rich Diamino‐bis(1H‐1,2,4‐triazole)

AbstractThe development of efficient catalysts for the dehydrogenation of formic acid (FA) through molecular level control and precise regulation remains challenging. Herein, we report the newly developed complexes of iridium and ruthenium with nitrogen‐rich ligand for aqueous FA dehydrogenation. The Cp*Ir complex 1 (Cp*=cyclopentadienyl) and Ru(p‐cym) complex 2 (p‐cym=p‐Cymene) were synthesized and fully characterized. The single crystal structures of these complexes have a typical piano‐stool structure. A turnover frequency of 12468 h−1 was achieved for FA dehydrogenation at 90 °C by using complex 1 bearing 3,3’‐diamino‐5,5’‐bis(1H‐1,2,4‐triazole) (DABT). The effects of pH, temperature, concentration of formic acid and amount of catalyst on the reaction kinetics were studied in detail. Kinetic isotope effect (KIE) experiments and 1H NMR detection of reaction revealed that a plausible mechanism involves the decarboxylation of formate and the formation of H2. More importantly, the influence of H2O and H+ was involved in the rate‐determining step. This study demonstrated the effectiveness of nitrogen‐rich ligand for FA dehydrogenation, which would contribute to the development of new and effective hydrogen release systems.

Arene Ruthenium(II)-Catalyzed Sustainable Synthesis of 2,4-Disubstituted Quinazolines via Acceptorless Dual Dehydrogenative Coupling of Alcohols.

We demonstrate an efficient and sustainable strategy for the direct synthesis of 2,4-disubstituted quinazolines by arene Ru(II)benzhydrazone complex via the eco-friendly sequential acceptorless dehydrogenative coupling of 2-aminobenzhydrol derivatives and benzyl alcohols for the first time. The new ruthenium(II) complex of the general formula [(η6-p-cymene)Ru(L1)Cl] (L1-acenaphthenequinone hydrazone) has been synthesized and characterized by analytical, spectroscopic, and single-crystal X-ray diffraction techniques. A broad spectrum of 2,4-disubstituted quinazolines have been successfully derived (25 examples) from 2-aminobenzhydrol derivatives with various benzyl alcohols using 1 mol % of catalyst loading in the presence of NH4OAc. The present protocol is highly selective and produces a maximum yield of 95% under mild reaction conditions. The different reaction intermediates detected through control experiments such as aldehyde, 2-aminobenzophenone, benzylidene(amino)phenylmethanone, and 1,2-dihydroquinazoline are isolated and authenticated by the NMR study. Gratifyingly, the coupling reaction is a simple and atom economic with the release of water and hydrogen gas as the only byproducts. A gram-scale synthesis of 2-(4-methoxyphenyl)-4-phenylquinazoline illustrates the synthetic utility of the present protocol.

Synthesis, Structural, and Quantum Chemical Analysis of Neutral and Cationic Ruthenium(II) Complexes with Nicotinate-Polyethylene Glycol Ester Ligands

Ruthenium(II/III)-based compounds have gained significant interest due to the biocompatibility of ruthenium, its similarity to iron, and the possibility for structural diversification through the choice of ligands. In this contribution, two novel ligands, (2-(2-methoxyethoxy)ethyl nicotinate hydrochloride) and (2-[2-(2-methoxyethoxy)ethoxy]ethyl nicotinate hydrochloride) (pyCOO(CH2CH2O)nCH3: L2, n = 2; L3, n = 3), were synthesized and characterized via ESI-HRMS, as well as IR and NMR spectroscopies. Their structures were optimized at the B3LYP/6-311++G(d,p) level of theory, and NMR chemical shifts were predicted, along with the most important intramolecular interactions. Additionally, two neutral complexes of the general formula [RuCl2(η6-p-cym) (L-κN)] (L = L2: 2; L3: 3) and two cationic complexes of the general formula [RuCl(η6-p-cym)(L-κN)2][PF6] (L = L1: 4; L2: 5) were obtained and characterized. The optimization of the structures was performed at the B3LYP/6-31+G(d,p)(H,C,N,O,Cl)/LanL2DZ(Ru) level of theory. Structural features were described, and intramolecular stabilization interactions were outlined.

Picket-fence ruthenium(II) phthalocyaninates bearing (1R,2S,5R)-menthoxy groups as prototype of chiral catalysts

We report design and synthesis of novel picket-fence phthalocyanines to access the ruthenium(II) complexes carrying di-(1R,2S,5R)-menthoxy substituted aryloxy-groups. Owing to bulkiness of such groups located either at peripheral (β) or non-peripheral (α) positions, they are nearly orthogonal to the plane of the phthalocyanine thus creating a chiral environment around the metal center. This orthogonality was supported by X-ray analysis of corresponding phthalonitrile precursors (86.0° and 81.4° angles between the planes of aromatic moieties for α- and β-substituted phthalonitriles, respectively). As a proof of concept, the synthesized complexes were investigated as catalysts in a benchmark reaction of the cyclopropanation of styrene by ethyl diazoacetate. While the β-substituted complex showed very low enantioselectivity, the α-substituted analogue afforded a moderate asymmetric induction towards ethyl (1S,2R)-2-phenylcyclopropane-1-carboxylate. This result emphasizes the importance of appropriate arrangement of the chiral groups relative to the phthalocyanine catalytic center and provides guidelines for further elaboration of phthalocyanine catalysts for asymmetric transfer of carbenes.

A Combination of Ruthenium Complexes and Photosensitizers to Treat Colorectal Cancer

Treatment regimens are regularly evolving alongside novel therapies and drugs. Such evolution is necessary to circumvent resistance mechanisms and to give patients the best possible health care. When dealing with cancer, most regimens involve multiple treatments (surgery, radiation therapy, chemotherapy, immunotherapy, etc.). The purpose of this study was to associate in a single compound metal-based drugs and photosensitizers to combine chemotherapy and photodynamic therapy. Two arene–ruthenium tetrapyridylporphyrin compounds (2H-TPyP-arene-Ru and Zn-TPyP-arene-Ru) have been synthesized and evaluated on two colorectal cancer cell lines (HCT116 and HT-29). Their cytotoxicity and phototoxicity have been evaluated. In addition, the anticancer mechanism and the cell death process mediated by the two compounds were studied. The results showed that the two arene–ruthenium photosensitizer-containing complexes have a strong phototoxic effect after photoactivation. The 2H-TPyP-arene-Ru complex induced outstanding cytotoxicity when compared to the Zn-TPyP-arene-Ru analogue. Moreover, under light, these two arene–ruthenium photosensitizers induce an apoptotic process in human colorectal cancer cell lines.

Antigen retrieval assisted electrochemiluminescence imaging of surface antigens at single tissue section

Previously, our group has established an electrochemiluminescence (ECL) molecular imaging method to detect carcinoembryonic antigen (CEA) at single tissue sections of carcinoma patients. However, the tissue fixation blocks the binding sites of surface antigens affecting the antigen-antibody interaction and the resultant visualization sensitivity. Herein, we report an antigen retrieval assisted ECL imaging strategy that utilizes heat-induced epitope retrieval (HIER) to re-expose the binding sites of the antigens for more efficient interaction between surface antigen and ruthenium-labeled antibody. With more ruthenium complexes tagged with surface antigens, the ECL intensity at the tissue sections increases significantly which could more accurately reflect the amount and the distribution of surface CEA. Accordingly, the different distribution of CEA at the carcinoma and paracancerous regions of tissue sections from two patients with lung adenocarcinoma (LUAD) is visualized, which could not be easily distinguished without the HIER treatment. Eventually, the combination of antigen retrieval and ECL molecular imaging could improve the visualization sensitivity at single tissue section and minimize the false negative phenomenon, which will greatly advance the development of ECL-based tissue imaging for future application in pathological diagnosis.

Ruthenium Complexes with N-Bound 2-Pyridonato Ligand as O-Donors: A New Synthetic Approach and the Effect on Reactivity.

In this study, Ru complexes [(η6-p-cymene)RuX(2-{(2,6-iPr2-C6H3)N=CH}-C5H3N-6-(O))] (3: X=Cl; 4: X=I) were prepared with N-bound 2-pyridonato ligand by thermal base-free MeX elimination from ionic N,N-chelated Ru complexes [(η6-p-cymene)RuX(κ2-L1)](X) (1: X=Cl; 2: X=I; L1={2-[(2,6-iPr2-C6H3)N=CH]-6-(OMe)C5H3N}). The Ru complex 3 was used as O-donor for Lewis (LA) or Brönsted acids. The reactions of 3 with SnCl2, Ph3SnCl, ZnCl2 or HCl provided [(η6-p-cymene)Ru(SnCl3)(2-{(2,6-iPr2-C6H3)N=CH}-C5H3N-6-(O→SnCl2)] (6), [(η6-p-cymene)RuCl(2-{(2,6-iPr2-C6H3)N=CH}-C5H3N-6-(O→SnPh3Cl)] (7), and [(η6-p-cymene)RuCl(2-{(2,6-iPr2-C6H3)N=CH}-C5H3N-6-(O→)]2(μ-ZnCl2) (8) and [(η6-p-cymene)RuCl(2-{(2,6-iPr2-C6H3)N=CH}-C5H3N-6-(OH)}](Cl) (9). The easy conversion of the 2-pyridonato ligand in 3 to its 2-hydroxypyridine in 9 evoked testing of 3 and 4 as potential catalysts in base-free transfer-hydrogenation of ketones.

Mechanistic Insight into Acceptorless Dehydrogenation of Methanol to Syngas Catalyzed by MACHO-Type Ruthenium and Manganese Complexes: A DFT Study.

The acceptorless dehydrogenation of methanol to produce carbon monoxide (CO) and dihydrogen (H2) mediated by MACHO-type 1-Ru and 1-Mn complexes was theoretically investigated via density functional theory calculations. The 1-Ru-catalyzed process involves the formation of active species 4-Ru through a methanol-bridged H2 release pathway. Methanol dehydrogenation by 4-Ru yields formaldehyde and 1-Ru, followed by H2 release to regenerate 4-Ru (rate-determining step, ΔG‡ = 32.5 kcal/mol). Formaldehyde further reacts with methanol via nucleophilic attack of the MeO- ligand in the Ru complex (ΔG‡ = 9.6 kcal/mol), which is more favorable than the traditional methanol-to-formaldehyde nucleophilic attack (ΔG‡ = 33.8 kcal/mol) due to the higher nucleophilicity of MeO-. CO is ultimately produced through the methyl formate decarbonylation reaction. Accelerated H2 release in the early reaction stage compared to CO results from the initial methanol dehydrogenation and condensation of formaldehyde with methanol. In contrast, CO generation occurs later via methyl formate decarbonylation. The 1-Mn-catalyzed reaction has reduced efficiency compared to 1-Ru for the higher Gibbs energy barrier (ΔG‡ = 34.1 kcal/mol) of the rate-determining step. Excess NaOtBu promotes the reaction of CO and methanol, forming methyl formate, significantly reducing the CO/H2 ratio as the catalyst amount decreases. These findings deepen our understanding of the methanol-to-syngas transformation and can drive progress in this field.

Ruthenium(II)-Arene Curcuminoid Complexes as Photosensitizer Agents for Antineoplastic and Antimicrobial Photodynamic Therapy: In Vitro and In Vivo Insights.

Photodynamic therapy (PDT) is an anticancer/antibacterial strategy in which photosensitizers (PSs), light, and molecular oxygen generate reactive oxygen species and induce cell death. PDT presents greater selectivity towards tumor cells than conventional chemotherapy; however, PSs have limitations that have prompted the search for new molecules featuring more favorable chemical-physical characteristics. Curcumin and its derivatives have been used in PDT. However, low water solubility, rapid metabolism, interference with other drugs, and low stability limit curcumin use. Chemical modifications have been proposed to improve curcumin activity, and metal-based PSs, especially ruthenium(II) complexes, have attracted considerable attention. This study aimed to characterize six Ru(II)-arene curcuminoids for anticancer and/or antibacterial PDT. The hydrophilicity, photodegradation rates, and singlet oxygen generation of the compounds were evaluated. The photodynamic effects on human colorectal cancer cell lines were also assessed, along with the ability of the compounds to induce ROS production, apoptotic, necrotic, and/or autophagic cell death. Overall, our encouraging results indicate that the Ru(II)-arene curcuminoid derivatives are worthy of further investigation and could represent an interesting option for cancer PDT. Additionally, the lack of significant in vivo toxicity on the larvae of Galleria mellonella is an important finding. Finally, the photoantimicrobial activity of HCurc I against Gram-positive bacteria is indeed promising.

Real-time investigation into thermal and photo decomposition of ruthenium complexes [Ru(acac)2(tmp-mian)] and [Ru(acac)2(tmp-bian)] in acetonitrile by aerodynamic thermal breakup droplet ionization mass spectrometry

Properties and mechanisms of thermal and photo decomposition of ruthenium complexes [Ru(acac)2(tmp-mian)] (1) and [Ru(acac)2(tmp-bian)] (2) [where acac = acetylacetonate, tmp = 2,4,6-{CH3}3C6H2, mian is monoiminoacenaphtheneone, and bian is acenaphthene-1,2-diimine] in acetonitrile were studied in real time by aerodynamic thermal breakup droplet ionization mass spectrometry (ATBDI-MS). A comparison of the ATBDI-MS spectra of complexes 1 and 2 showed a difference between photolysis processes in these structurally similar complexes because the Ru–O– bond in complex 1 is much weaker than the Ru–N bond in complex 2. This difference leads to easier decomposition of complex 1 and facilitates the capture of solvent molecules by products of complex 1′s photolysis. Similarly, the analysis of thermal decomposition of complexes 1 and 2 at increasing temperatures of an ATBDI suction tube (Tsuction) showed that complex 1 is much more susceptible to thermal decomposition and starts to disintegrate already at 100 °C. Complex 2 is much stabler; there was no evidence of its thermal decomposition when Tsuction was raised up to 330 °C.

Gelatin Carbon Dots Interaction with Nitrosyl Ruthenium Complex: Fluorescence Quenching and Chemiluminescence Mechanisms.

Carbon dots (CDs) exhibit luminescence, biocompatibility, and higher water solubility. This material has been developed for biological applications, specifically in bioimaging. In this work, the gelatin carbon dots (CDg) was obtained from commercial gelatin using a hydrothermal method in domestic microwave, and the suppression fluorescent mechanism were enhanced by the addition of the [RuII(bdq)(NO)(tpy)]3+ (Rubdq-NO+) complex ion. After purification through a dialysis bag, the resulting CDs (CDg) exhibit fluorescent emission at 400nm and maintained fluorescence stability in an aqueous solution (pH = 7) for 30days under 5 ◦C. Fluorescence quenching studies revealed an electrostatic interaction between the negative charge from CDg (δ = - 20mV) and the positively charged nitrosyl (NO+) ligand of the ruthenium complex (Rubdq-NO+), resulting in quenching of the CDg fluorescence due to the inner filter effects (IFE). The chemiluminescence reaction of CDg and Rubdq-NO-CDg in presence of norepinephrine (NOR) were evaluated. NOR in PBS are liable to undergo spontaneous oxidation to quinone form (NOR-quinone). CDg are believed interact with NOR-quinone and an electron transfer occur obtained CDg+ accompanied to green emission fluorescence (520nm). While for Rubdq-NO-CDg in presence of NOR, the green emission occurs accompanied by NO0 release using DAF-2 probe.

EVALUATION OF THE POTENTIAL CYTOTOXICITY OF RUTHENIUM COMPLEX II AGAINST U-373 GLIOBLASTOMA CELLS

Objective: The potential of ruthenium complexes as anticancer agents has gained significant attention in the scientific community. The aim of this study was to investigate the effect of dithiocyanato-N-bis[8(diphenylphosphino)quinoline]ruthenium (II), [Ru(N-P)2(NCS)2] on the glioblastoma U-373 tumor cells and apoptosis. Methods: Ru(N-P)2(NCS)2] was synthesized and characterized using FTIR, and X-ray crystallography. The cytotoxic effects of [Ru(N-P)2(NCS)2] on glioblastoma U-373 tumor cells were evaluated using both the trypan blue assay and the activity of caspase-3 to detect apoptosis. A DPPH scavenging assay was used to evaluate the antioxidant activity. Results: The [Ru(N-P)2(NCS)2] complex effectively inhibited the glioblastoma U-373 tumor cells with an IC50 of ~ 23 µg/ml. Similar to the majority of chemotherapeutic agents that kill via the intrinsic pathway, [Ru(N-P)2(NCS)2] induces apoptosis, which was confirmed by the activation of caspase-3, and these effects were dose-dependent. Ruthenium has antioxidant properties, so ruthenium Complex II exhibits lower toxicity towards normal cells while effectively targeting and eliminating cancer cells. Conclusion: [Ru(N-P)2(NCS)2] is considered promising for researchers investigating putative biological activities, particularly antitumor and immune-related activity.

Finding the best location: Improving the anti-amyloid ability of ruthenium(III) complexes with pyridine ligands

Alzheimer's disease (AD) is a devastating neurological disorder where one of the primary pathological hallmarks are aggregate deposits of the peptide amyloid-beta (Aβ). Although the Food and Drug Administration (FDA) has recently approved therapeutics that specifically target Aβ, resulting in the removal of these deposits, the associated costs of such treatments create a need for effective, yet cheaper, alternatives. Metal-based compounds are propitious therapeutic candidates as they exploit the metal-binding properties of Aβ, forming stable interactions with the peptide, thereby limiting its aggregation and toxicity. Previously, ruthenium-based complexes have shown a strong ability to modulate the aggregation and cytotoxicity of Aβ, where the incorporation of a primary amine on the coordinated heterocyclic ligand gave the greatest activity. To determine the importance of the location of the primary amine on the pyridine ligand, thereby establishing structure-activity relationships (SAR), four complexes (RuP1–4) were prepared and evaluated for their ability to coordinate and subsequently modulate the aggregation and cytotoxicity of Aβ. Coordination to Aβ was determined using three complementary spectroscopic methods: UV–Vis, 1H NMR, and circular dichroism (CD). Similarly, the impact of the complexes on Aβ aggregation was evaluated using three sequential methods of turbidity, dynamic light scattering (DLS), and transmission electron microscopy (TEM). Overall, the location of the primary amine on the pyridine ligand did affect the resultant anti-Aβ performance, with the 2-aminopyridine complex (RuP2) being the most active. This SAR will provide another guiding principle in the design of future metal-based anti-Aβ complexes.

Studies of κ2- and κ3-tripyridylamine complexes of ruthenium and π-stacking by pyridyls.

The reaction of tris(pyridin-2-yl)amine with [CyRuCl2]2 (Cy = p-isopropyltoluene or cymene) in refluxing diglyme led to the formation of cis-[RuCl2{κ2-(2-py)3N}2]·CHCl3 (1a) after recrystallization from chloroform/pentane, or cis-dichloridobis[tris(pyridin-2-yl)amine-κ2N,N']ruthenium(II) dichloromethane disolvate, [RuCl2(C15H12N4)2]·2CH2Cl2 or cis-[RuCl2{κ2-(2-py)3N}2]·2CH2Cl2 (1b). Treatment of 1a with one equivalent of silver(I) hexafluoridoantimonate in dichloromethane gave [RuCl{κ2-(2-py)3N}{κ3-(2-py)3N}][SbF6]·CH2Cl2 (2a). Crystallization of 2a from chloroform provided chlorido[tris(pyridin-2-yl)amine-κ2N,N'][tris(pyridin-2-yl)amine-κ3N,N',N'']ruthenium(II) hexafluoridoantimonate chloroform monosolvate, [RuCl(C15H12N4)2][SbF6]·CHCl3 or [RuCl{κ2-(2-py)3N}{κ3-(2-py)3N}][SbF6]·CHCl3 (2b). Complex 2a reacted with a further equivalent of silver(I) hexafluoridoantimonate to give [Ru{κ3-(2-py)3N}2][SbF6]2 (3). The reaction of (2-py)3N with [CyRuCl2]2 in dichloromethane followed by treatment with excess sodium hexafluoridoantimonate gave the known complex [CyRuCl{κ2-(2-py)3N}][SbF6] (4). Complex 2 is a rare example of a complex containing both κ2- and κ3-(2-py)3N. Intramolecular π-stacking interactions determine the orientation of the free pyridyl in the κ2 complexes. An interesting encapsulation of methylene chloride hydrogen-bonded tetramers was noted in one case.

Anticancer Properties of Ru and Os Half-Sandwich Complexes of N,S Bidentate Schiff Base Ligands Derived from Phenylthiocarbamide.

The versatile coordinating nature of N,S bidentate ligands is of great importance in medicinal chemistry imparting stability and enhancing biological properties of the metal complexes. Phenylthiocarbamide-based N,S donor Schiff bases converted into RuII /OsII (cymene) complexes and characterized by spectroscopic techniques and elemental analysis. The hydrolytic stability of metal complexes to undergo metal-halide ligand exchange reaction was confirmed both by the DFT and NMR experimentation. The ONIOM (QM/MM) study confirmed the histone protein targeting nature of aqua/hydroxido complex 2 aH with an excellent binding energy of -103.19 kcal/mol. The antiproliferative activity against a panel of cancer cells A549, MCF-7, PC-3, and HepG2 revealed that ruthenium complexes 1 a-3 a were more cytotoxic than osmium complexes and their respective ligands 1-3 as well. Among these ruthenium cymene complex bearing sulfonamide moiety 2 a proved a strong cytotoxic agent and showed excellent correlation of cellular accumulation, lipophilicity, and drug-likeness to the anticancer activity. Moreover, the favorable physiochemical properties such as bioavailability and gastrointestinal absorption of ligand 2 also supported the development of Ru complex 2 a as an orally active anticancer metallodrug.

An Anthracene-Thiolate-Ligated Ruthenium Complex: Computational Insights into Z-Stereoselective Cross Metathesis.

Stereoselective control of the cross metathesis of olefins is a crucial aspect of synthetic procedures. In this study, we utilized density functional theory methods to calculate thermodynamic and kinetic descriptors to explore the stereoselectivity of cross metathesis between allylbenzene and 2-butene-1,4-diyl diacetate. A ruthenium-based complex, characterized primarily by an anthracene-9-thiolate ligand, was designed in silico to completely restrict the E conformation of olefins through a bottom-bound mechanism. Our investigation of the kinetics of all feasible propagation routes demonstrated that Z-stereoisomers of metathesis products can be synthesized with an energy cost of only 13 kcal/mol. As a result, we encourage further research into the synthetic strategies outlined in this work.

A Ruthenium(II) complex based long lifetime phosphorescent probe for copper ions and pH detection

ObjectiveTransition metal ruthenium(II) complex was used to prepare a dual-functional phosphorescent probe for the detection of Cu2+ ion and pH. MethodsThe ligand (E)-6-((thiazol-2-yl methylene)amino)-1,10-phenanthrolin-5-amine (tmpa) was prepared by condensation of 5,6-diamine-1, 10-phenanthroline with 2-formylthiazole, and then ruthenium(II) complex [Ru(bpy)2tmpa](PF6) (Ru-tmpa, bpy ​= ​2,2′-bipyridine) was synthesized by the coordination of tmpa with cis-Ru(bpy)2Cl2. Phosphorescence spectra were measured to investigate its response to metal ions (Li+, Na+, K+, Mg2+, Ca2+, Mn2+, Pb2+, Cr2+, Co2+, Ni2+, Cu+, Cu2+, Fe3+, Fe2+ and Zn2+). The binding affinity and detecting limit of Ru-tmpa to copper ions were tested by titration experiment. The ability of the probe to monitor copper ion levels inside cells was tested by confocal microscopy imaging. ResultsRu-tmpa can rapidly, sensitively and selectively detect Cu2+ in water and biological sample, and shows a sensitive phosphorescence response to pH. Ru-tmpa can penetrate cell membrane, enter the cell, and monitor the level of copper ions inside cell. ConclusionA novel fluorescent probe Ru-tmpa was synthesized to provide a powerful tool for the detection of Cu2+ and pH in biological and environmental systems.

A Comprehensive Review for Ruthenium(II) Complexes in Photodynamic Therapy

Photodynamic therapy (PDT) has emerged as a promising therapeutic approach for the treatment of various diseases, including cancer. In recent years, ruthenium(II) complexes have garnered significant interests as photsensitizers in PDT due to their unique photophysical properties and versatile coordination chemistry. The current developments in the use of Ru(II) complexes as photosensitizers in PDT are thoroughly examined in this review article. The design techniques used to increase their photodynamic effectiveness, increase selectivity and reduce off-target impacts are discussed. The formation of reactive oxygen species (ROS) and the ways in which they influence biological processes are also being explored. Additionally, the Ru(II) complexes with dual functioning, targeting abilities and uses in various disease models are highlighted. Prospects and challenges in this area such as water solubility, biocompatibility and translational issues are discussed. The goal of this review article is to provide a thorough overview of the potential of Ru(II) complexes in PDT and to inspire additional investigation in this fascinating field.

Benzimidazol-2-ylidene ruthenium complexes for C-N bond formation through alcohol dehydrogenation.

A low temperature hydrogen borrowing approach to generate secondary amines using benzimidazole-based N-heterocyclic carbene (BNHC) ruthenium complexes is reported. A series of the piano-stool complexes of the type [(η6-p-cymene)(BNHC)RuCl2] (1a-g) were synthesized via one-pot reaction of the NHC salt precursor, Ag2O, and [RuCl2(p-cymene)]2 and characterized using conventional spectroscopic techniques. The geometry of two precursors, [(η6-p-cymene)(Me4BnMe2BNHCCH2OxMe)RuCl2] (1f) and [(η6-p-cymene)(Me5BnMe2BNHCCH2OxMe)RuCl2] (1g), was studied by single crystal X-ray diffraction. These catalysts were found to dehydrogenate alcohols efficiently at temperatures as low as 50 °C to allow Schiff-base condensation and subsequent imine hydrogenation to afford secondary amines. Notably, this ruthenium-based procedure enables the N-alkylation of aromatic and heteroaromatic primary amines with a wide range of primary alcohols in excellent yields of up to 98%. The present methodology is green and water is liberated as the sole byproduct.