Metal Complexes Research Articles

Advanced computational screening of X2CaH4 (X = Rb and Cs) for hydrogen storage applications

Utilizing cutting-edge computational screening methods, this study explores the hydrogen storage capacity of two complex metal hydrides, Cs2CaH4 and Rb2CaH4. We perform a thorough analysis of their structural, electrical, optical, and hydrogen storage properties using density functional theory (DFT). Within the I4/mmm space group, both compounds display stable tetragonal crystal structures, and their thermodynamic stability is confirmed by their formation energies. Notably, compared to Rb2CaH4, Cs2CaH4 is more stable. With band gaps of 2.99 eV for Cs2CaH4 and 3.28 eV for Rb2CaH4, the electronic properties show insulating behavior, which is beneficial for reducing electronic interference during hydrogen absorption and desorption. A comparative research reveals that the potential gravimetric hydrogen storage capacities of Cs2CaH4 (1.28%) and Rb2CaH4 (1.86%) are comparable to, albeit marginally less than, those of materials that are frequently explored, such as lithium borohydride. With their individual absorption and reflectivity peaks, the optical characteristics offer more information about how they interact with electromagnetic radiation, information that may be useful for improving their performance in real-world applications. Our results imply that Cs2CaH4and Rb2CaH4 have considerable potential for use in practical hydrogen storage systems, especially in situations where stability and minimal electronic interference are essential. Subsequent research endeavors may concentrate on enhancing the hydrogen storage capacity of these materials, so rendering their incorporation into existing hydrogen storage methods more feasible.

Improving the Accuracy in the Prediction of Transition-Metal Spin-State Energetics Using a Robust Variation-Based Approach: Density Functional Theory, CASPT2 and MC-PDFT Applied to the Case Study of Tris-Diimine Fe(II) Complexes.

Designing ligands for transition metal complexes with a specified low-spin, high-spin or spin-crossover behavior is challenging. A major advance was recently made by Phan et al. [J. Am. Chem. Soc. 2017, 139, 6437-6447] who showed that the spin state of a homoleptic tris-diimine Fe(II) complex can be predicted from the N-N distance in the free diimine. They could thus predict the change in magnetic behavior on passing from the complexes of 2,2'-bipyridine (bpy), 2,2'-biimidazole (bim) and 2,2'-bis-2-imidazoline (bimz) ligands to those obtained with the modified analogs 4,5-diazafluoren-9-one (dafo), 1,1'-(α,α'-o-xylyl)-2,2'-bisimidazole (xbim) and 2,3,5,6,8,9-hexahydrodiimidazo[1,2-a:2', 1'-c]pyrazine (etbimz), respectively. Theoretically, the challenge lies in the accurate determination of the HS-LS zero-point energy difference ΔEHL°. The issue can be circumvented by using a variation-based approach, wherein ΔEHL° is not directly evaluated but obtained from the estimate of its variation Δ(ΔEHL°) in series of related systems, which include one whose ΔEHL° is accurately known [Phys. Chem. Chem. Phys. 2013, 15, 3752-3763; J. Phys. Chem. A 2022, 126, 6221-6235]. In this study, density functional theory (DFT), second-order multireference perturbation theory in its CASPT2 formulation, multiconfigurational pair DFT (MC-PDFT) and its hybrid formulation (HMC-PDFT) have been applied to the determination of Δ(ΔEHL°) in the pairs of complexes , , , and , . In DFT, we used several semilocal functionals and their global hybrids, as well as their D2, D3, D3BJ and D4 dispersion-corrected forms; and in MC-PDFT, different translated and fully translated functionals. The results are consistent with one another and in very good agreement with experiments. They show small to vanishing dependence on key details of the methods used: namely, the exact-exchange contribution to global hybrids; the ionization potential-electron affinity shift and basis sets used in the CASPT2 calculations; and the active spaces employed for the CASSCF wave functions used in the MC-PDFT and HMC-PDFT calculations. Insights into the change in the spin-state energetics accompanying the ligand exchanges were gained through a complexation energy analysis. Using the accurate CCSD(T) estimate of the HS-LS adiabatic energy difference in [J. Chem. Theory Comput. 2012, 8, 4216-4231], the Δ(ΔEHL°)-approach has been applied to the determination of ΔEHL° in the diimine complexes. The CASPT2 and DFT-D2 methods only give results in agreement with experiments. This suggests for the other methods a limitation in their treatment of dispersion which prevents them from accurately describing the spin-state energetics change accompanying the passing from with the tetragonal arrangement of its nitrile ligands to the tris-diimine complexes with the trigonal packing of their bulkier ligands.

Optimised syntheses and purifications of 3-aryl/heterocyclic dihydrobis- and hydrotris-(pyrazolyl)borate ligands as their alkali salts.

Though poly(pyrazolyl)borate ligands, namely dihydrobis(pyrazolyl)borate (Bp) and hydrotris(pyrazolyl)borate (Tp), have been used in coordination chemistry for decades, their synthesis and purification are of great importance, when targeting high purity and yield of metal complexes. As borohydride substitutions is temperature and pyrazolyl dependent, determining the reaction conditions for each ligand is non-trivial and does not always result in a temperature where only the desired products form. Herein we report the purification of two known TpR (R = phenyl, 2'-thienyl), as their tris-substituted temperatures coincide with their tetrakis-temperatures via fraction crystallisation from MeCN, and an optimised safe procedure for 3-aryl/heterocyclic BpR ligands (R = 2'-pyridyl, 2'-furyl, 2'-thineyl). These novel techniques allow for the safe isolation of alkali salts of poly(pyrazolyl)borate ligands in high yields and purities without the use of highly toxic thallium(i) salts.

Carbon dioxide as a sustainable reagent in circular hydrometallurgy.

This review highlights the use of CO2 as a reagent in hydrometallurgy, with emphasis on the new concept of circular hydrometallurgy. It is shown how waste CO2 can be utilised in hydrometallurgical operations for pH control or regeneration of acids for leaching. Metal-rich raffinate solutions generated after removal of the valuable metals can serve as feedstocks for mineral carbonation, providing alternative avenues for CO2 sequestration. Furthermore, CO2 can also be used as a renewable feedstock for the production of chemical reagents that can find applications in hydrometallurgy as lixiviant, as precipitation reagent or for pH control. Mineral carbonation can be combined with chemical reactions involving metal complexation reagents, as well as with solvent extraction processes for the concurrent precipitation of metal carbonates and acid regeneration. An outlook for future research in the area is also presented.

Effect of heat input on ultrahard Fe-Cr-B-C-W-Mo-Nb hardfacing

Multicomponent alloys (Cr, Mo, W, Nb, C, B) nanostructured iron base with complex carboborides have been developed to provide great protection against abrasive wear to elements of agricultural and mining machines. These overlays are subject to severe material losses due to impact and abrasion of hard particles and therefore optimizing their wear resistance is critical when it comes to their lifespan, increasing it as a result. The objective of this work was to study the influence of heat input on the wear resistance through of the analysis of the solidification rate. In this sense, the increase of welding speed was produced a decrease of heat input and refined of microstructure. In order to explain these effects, an analysis was made of of the influence of welding speed on the geometry of the deposited metal, dilution with the base metal, microstructural evolution and hardness of iron-based nanostructured deposits with complex carbides. For this, four samples were welded with different speeds; these being 1, 2.5, 5 and 12 mm/s. A semi-automatic welding process was used with a 1.6 mm wire rope used to provide gas protection. The chemical composition was analyzed on a dilution free welded sample. For the each welded sample the dilution percentage was determined, the dimensional survey of the beads was carried out and the microstructure was characterized by X-ray diffraction and optical and scanning electron microscopy. In addition, Vickers microhardness tests were measured in the central area of the beads and the microhardness of phases were measured. The dilution of the deposited metals ranged from 17% to a maximum of 28%. A microstructure formed by a matrix with complex metal carbides and carboborides was observed. The hardness of the beads varied between 960 and 1350 HV2. The highest wear resistance was found in the sample with highest speed welding.

Unsymmetrical ferrocene-based azines: Facile synthesis, investigation of spectral and electrochemical properties, and antibacterial activity

Ferrocenyl azines have been utilized in metal ion detection, as a ligand in the synthesis of metal complexes, in catalysis, in dye-sensitized solar cells, and in studies on antiparasitic, antitumor, and antileishmanial. However, most of the challenging synthesis routes require temperature control, expensive starting materials, and additional steps. In this research, a series of new unsymmetrical ferrocene-based azines (2a-j and 4a-j) were simply synthesized from the reaction of ferrocenecarboxaldehydehydrazone (1) and 1,1′-ferrocenedicarboxaldehydehydrazone (3) with various aryl aldehydes in moderate to good yield (40–80 %). All compounds were characterized using FT-IR, 1H and 13C NMR, and LC-MS. In addition, the molecular structure of 2b and 2h were determined by X-ray structure analysis. UV–Vis spectra of azines revealed weak absorbance in the 460–490 nm region for the d → d transition of Fe(II) and two strong absorbances in the range of 250–350 nm for π → π* and n → π* of aromatic rings and azine bridges. Cyclic voltammetry demonstrated higher half-wave potentials (E1/2) for all ferrocenyl azines in comparison to ferrocene as the internal standard, with a significant decrease of E1/2 for ferrocenyl-rich derivatives. The antibacterial activities of all synthesized ferrocenyl azines were also investigated against Staphylococcus aureus (gram-positive) and Escherichia coli (gram-negative) bacteria. Two ferrocene-rich compounds, 2i and 4j, have shown significant activity against Staphylococcus aureus.

Hybrid Hydroxyapatite-Metal Complex Materials Derived from Amino Acids and Nucleobases.

Calcium phosphates (CaPs) and their substituted derivatives encompass a large number of compounds with a vast presence in nature that have aroused a great interest for decades. In particular, hydroxyapatite (HAp, Ca10(OH)2(PO4)6) is the most abundant CaP mineral and is significant in the biological world, at least in part due to being a major compound in bones and teeth. HAp exhibits excellent properties, such as safety, stability, hardness, biocompatibility, and osteoconductivity, among others. Even some of its drawbacks, such as its fragility, can be redirected thanks to another essential feature: its great versatility. This is based on the compound's tendency to undergo substitutions of its constituent ions and to incorporate or anchor new molecules on its surface and pores. Thus, its affinity for biomolecules makes it an optimal compound for multiple applications, mainly, but not only, in biological and biomedical fields. The present review provides a chemical and structural context to explain the affinity of HAp for biomolecules such as proteins and nucleic acids to generate hybrid materials. A size-dependent criterium of increasing complexity is applied, ranging from amino acids/nucleobases to the corresponding macromolecules. The incorporation of metal ions or metal complexes into these functionalized compounds is also discussed.

Advanced electrochemical oxidation of EDTA-Ni via cobalt single-atom catalysts: Exploring indirect persulfate activation pathways

This study explores an innovative electrochemical strategy for the removal of the highly stable and toxic EDTA-Ni complex found in electroplating wastewater. Utilizing a cobalt-based single-atom catalyst (Co-NC) in an electro-enhanced system, we achieved significant activation of peroxydisulfate (PDS) for effective degradation of EDTA-Ni. Under optimal conditions of 40 mA current density and a pH range of 3–7, more than 97% of EDTA-Ni (1 mM) was successfully degraded within 90 min. Through detailed electrochemical experiments, we identified that atomic hydrogen (H*) played a crucial role in the indirect activation of PDS, facilitating the formation of reactive sulfate radicals (·SO4-). Computational analysis using density functional theory (DFT) confirmed that the H*-mediated reduction pathway had a notably low energy barrier (ΔGbs = 0.51 eV), making it the dominant activation mechanism. Gas chromatography-mass spectrometry (GC–MS) further revealed the primary degradation intermediates, providing insights into the breakdown process of EDTA-Ni. This research underscores the potential of Co-NC catalyst as a highly effective catalyst for treating persistent heavy metal complexes in advanced oxidation systems.

Enhanced nanocellulose extraction from date palm waste: green solvent hydrolysis with transition metal complex

This study presents a novel method for nanocellulose production using [Bmim]Cl as a green solvent, with enhanced hydrolysis efficiency achieved through the addition of a transition metal complex as a catalyst. The redox capability of the transition metal complex to break the glycosidic bonds in cellulose is amplified by the addition of an oxidizing agent. This protocol represents the latest innovation in the field of nanocellulose production, resulting in improved yield and reduced particle size. Nanocellulose (NC) was extracted from date seeds using 1-butyl-3-methylimidazolium chloride [Bmim]Cl coupled with a transition metal complex comprising copper metal and pyridine as a ligand along with H2O2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\ ext{H}}_{2}{\ ext{O}}_{2}$$\\end{document} as an oxidizing agent. Unlike conventional [Bmim]Cl hydrolysis, which typically yields only microcrystalline cellulose (MCC), this approach resulted in a 25% higher yield of NC than that of MCC. Dynamic light scattering analysis showed a substantial reduction in hydrodiameter from 1200 nm for MCC to 128.7 nm for NC, highlighting the remarkable efficiency of this process. Thermal analysis demonstrated the high stability of NC, which showed a Tonset\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${T}_{onset}$$\\end{document} of 286 °C and an activation energy (Ea\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${E}_{a}$$\\end{document}) of 220.41 kJ/mol. X-ray diffraction analysis indicated that NC possessed a high degree of crystallinity (Crl=\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${C}_{rl}=$$\\end{document} 70.28%). Furthermore, NC underwent modification with 3-aminopropyltriethoxysilane to replace free hydroxyl groups (–OH), making it redispersal and suitable for various applications. This modification was confirmed through Fourier transform infrared spectroscopy, which showed the presence of characteristic functional groups, and energy-dispersive X-ray spectroscopy, which verified the elemental composition. Zeta potential measurements revealed surface charge differences, with MCC at − 27.87 mV, NC at − 27.28 mV, and modified NC at − 44.72 mV, indicating improved colloidal stability after modification. These findings highlight the protocol's effectiveness and its potential impact on the NC production industry, offering improved yields and the production of nanosized fibers using green solvents.

Di-μ-adipato-κ4 O 1,O 1':O 6,O 6'-bis-[(2,2'-di-pyridyl-amine-κ2 N,N')zinc(II)] trihydrate.

The title compound, [Zn2(C6H8O4)2(C10H9N3)2]·3H2O or {Zn2[(C5H4N)2NH]2[μ-(CH2)4(COO)2]2}·3H2O, was separ-ated from the solvothermal reaction of zinc(II) sulfate hepta-hydrate, 2,2'-di-pyridyl-amine and sodium adipate. The dinuclear metal complex has a centrosymmetric structure, with the ZnII atom adopting a highly distorted octa-hedral coordination sphere composed of four oxygen atoms from bridging adipato ligands and two pyridine nitro-gen atoms. In the crystal, the title compound aggregates into a tri-periodic supra-molecular structure through inter-molecular hydrogen-bonding networks of the form O-H⋯O and N-H⋯O.

Metal Complexes of Cobalt Chloride with Vinyl‐, Allyl‐ and Styrylbenzimidazole Ligands: Synthesis, Structure, and Properties

AbstractThree N‐substituted benzimidazole cobalt(II) complexes have been synthesized and fully characterized by elemental analysis, FT‐IR spectroscopy, and X‐ray crystallography. The crystal packing formation features were studied by AIM analysis, and the energy and nature of both weak noncovalent interactions in the crystal and metal–ligand coordination bonds were assessed. These N‐coordinated cobalt(II) complexes were screened for antimicrobial activities against Gram‐negative (Escherichia coli, Bacillus subtilis) and Gram‐positive (Enterococcus durans) bacteria. Minimal inhibitory concentrations (MIC = 6.2 mg/mL) were found for complex cobalt chloride with allylbenzimidazole ligands against E. durans and E. coli. Its antimicrobial activity is several times higher compared to the reference gentamicin. Molecular docking made it possible to consider the nature of binding of cobalt metal complexes with vinyl‐, allyl‐ and styrylbenzimidazole ligands to biological targets and estimate their energy. The binding energy meanings depend on protein and ligand type, and reaches 8 kcal/mol.

A comprehensive review on the development of chiral Cu, Ni, and Zn complexes as pharmaceutical agents over the past decades: Synthesis, molecular structure and biological activity.

Chirality is a fundamental and widespread geometric structural property in living organisms that most biomacromolecules including nucleic acids, proteins and enzymes, possess. Consequently, the development of chiral drugs capable of binding specific targets have gradually gained wide attention in recent decades due to their selective effects on a broad spectrum of biological events ranging from cell metabolism to cell fate. In this context, the synthesis of chiral compounds as promising therapeutic candidates has assumed a major role in drug discovery. Among them, chiral metal complexes have attracted considerable interest due to their unique and intriguing structural features that could enable overcoming side effects and drug-resistance phenomena of metal-based drugs currently in the market such as cisplatin. In the current scenario, an in-depth overview of non-platinum chiral complexes needs to be presented and carried forward. Therefore, in this perspective article, an update of the scientific development of bioactive chiral copper, zinc and nickel complexes have been reported since they have not been thoroughly reviewed so far. Specifically, we focused the article mainly on metal complexes containing chiral ligands (type 2 chirality) as in literature they are more numerous than those with chirality at the metal center (type 1 chirality). Herein, not only their biological activity but also their mechanism of action is summarized. Furthermore, in the final section of the article we have highlighted copper-based complexes as those with a superior biological activity profile and greater prospects for development as a drug.

Exploration of newly synthesized transition metal(II) complexes for infectious diseases.

Aim: In the annals of human history, infectious diseases significantly influencing the collective well-being of people worldwide. Consequently, to identify effective agents for infectious ailments, the octahedral Co(II), Ni(II), Cu(II), Zn(II) complexes of 4-(3-methoxyphenyl)pyrimidin-2-amine and 2-methoxy-1-napthaldehyde based ligand were synthesized and well characterized in the current investigation.Results & methodology: The synthesized compounds were evaluated for anti-TB, anti-inflammatory, antibacterial, antifungal activities by microplate Alamar blue, bovine serum albumin, serial dilution assays. The [Zn(L1)2(H2O)2] complex (5) demonstrates robust potency with 0.0040±0.0007 and 0.0038μmol/ml MIC value in anti-tuberculosis and antimicrobial activities, correspondingly while 06.57±0.03μM IC50 value in anti-inflammatory investigation.Conclusion: Complex (5) show promising potential as targets for pathogen deformities, supported by rigorous biological and computational investigations including pharmacophore modelling, molecular docking (binding score -121.018 and -59.8662kcal/mol for 6H53 and 1CX2 proteins, respectively), DFT (Density functional theory), MESP (MolecularElectrostaticPotential) and ADMET (absorption, distribution, metabolism, excretion and toxicity).

Photo- and Electrocatalytic Hydrogen Evolution by Heteroleptic Dirhodium(II,II) Complexes: Role of the Bridging and Diimine Ligands.

A series of heteroleptic Rh2(II,II) complexes, cis-[Rh2(μ-DPhF)2(μ-bncn)2]2+ (1; bncn = benzo[c]cinnoline), cis-[Rh2(μ-DPhF)(μ-OAc)(μ-bncn)2]2+ (2), and cis-[Rh2(μ-OAc)2(μ-bncn)2]2+ (3), is presented, and the excited state and redox properties of each complex was characterized for the photo- and electrocatalytic production of H2. The oxidation potentials shift anodically from 1 to 3, consistent with a highest occupied molecular orbital (HOMO) with significant metal-ligand mixing, Rh2(δ*)/DPhF(π/nb). In contrast, modest differences in the first two bncn-localized reversible reduction potentials were observed in 1 - 3. The lowest energy metal/ligand-to-ligand charge transfer (1ML-LCT) transition, Rh2(δ*)/DPhF(π/nb) → bncn(π*), shifts from 633 nm in 1 to 553 nm in 2, and the metal-to-ligand charge transfer (1MLCT) Rh2(π*) → bncn(π*) absorption in 3 appears at 462 nm in CH3CN. Although the 3ML-LCT excited state of 2 is shorter lived than that of 1, 2.7 ns as compared to 19 ns, respectively, photocatalytic hydrogen generation is observed for the former upon 595 nm irradiation in the presence of 0.1 M TsOH (p-tolylsulfonic acid) and 0.1 M BNAH (1-benzyl-1,4-dihydronicotinamide). The temperature dependence of the 3ML-LCT lifetimes of 1 and 2 shows the presence of a thermally accessible deactivating state. In addition, the singly reduced intermediate, [2]-, is photoactive and able to generate hydrogen in the presence of TsOH. Importantly, the electrocatalytic currents generated by equimolar concentrations of 1 - 3 in CH3CN are nearly identical, consistent with a mechanism of catalysis that is localized on the bncn ligand and does not require a Rh-H hydride intermediate. This finding can be used to develop earth-abundant first-row transition metal complexes for photo- and electrocatalytic H2 production.

Alternative of cisplatin - Introduction of rhodium analogues

The use of transition metal complexes as anti-cancer agents became most practiced since the discovery and approval of cis-platin in 1978. Different analogues of platinum complexes were discovered and further investigated to find maximum efficiency on the target. But it was soon realized, the Pt-complexes had numerous side effects like resistance, neurotoxicity, etc. by which they couldn't reach to their final expectation. Hence, scientists researched other efficient alternatives, which can defeat the limitations of platinum analogues and shows capability in induced tumour cell death. In this review, we attempted to discuss how rhodium analogues can be a better alternative than cis-platin as an anti-cancer agent.

Metal complexes containing vitamin B6-based scaffold as potential DNA/BSA-binding agents inducing apoptosis in hepatocarcinoma (HepG2) cells.

A ligand (HL) was synthesized from the pyridoxal hydrochloride (vitamin B6 form) and 1-(2-Aminoethyl)piperidine in one single step. The metal complexes [Zn(L)(Bpy)]NO3 (1), [Cu(L)(Bpy)]NO3 (2), and [Co(L)(Bpy)]NO3 (3) were prepared by tethering HL and 2,2'-bipyridine. The synthesized HL and metal complexes 1-3 were thoroughly characterized using spectroscopic techniques such as 1H NMR, 13C NMR, FTIR, EI-MS, molar conductance, and magnetic moment, in addition to CHN elemental analysis. The geometry of complexes was square pyramidal around the metal ions {Zn(II), Cu(II), and Co(II)}. The interaction of ligand and metal complexes with DNA and BSA macromolecules was accomplished by UV-Vis absorption and fluorescence spectroscopy in vitro. The hyperchromism in band at 303-325 with no shift supports the groove binding with some partial intercalation in grooves. Similarly, in BSA-binding studies, complex 2 shows greater binding potential in the hydrophobic core probably near the Trp-212 in the subdomain IIA. Furthermore, complex 2 shows excellent cytotoxicity on HepG2 cancer cells with IC50 = 25.0 ± 0.45µM. The detailed analysis by cell-cycle studies shows cell arrest at the G2/M phase. The type of cell death was authenticated by an annexin V-FTIC dual staining experiment that reveals maximum death by apoptosis together with non-specific necrosis.

Synthesis, Characterization, and Catalysis of Planar Chiral Ferrocene‐based N‐Heterocyclic Carbene Ligands and Its Metal Complexes

This study presents the development of a novel planar chiral ferrocene‐based NHC ligand and its corresponding metal complexes. The key unit of the imidazolium backbone, planar chiral ortho‐isopropyl ferrocenyl amine, was synthesized starting from (R)‐Ugi's amine. Imidazolium was obtained through the sequential condensation of glyoxal with ferrocenyl amine, followed by the ring‐closure of 1,3‐diferrocenyldiimine with chloromethylethyl ether. Chiral imidazolylidene NHC (IFcPr) metal complexes were prepared by treating imidazolium with silver oxide or base followed by transmetalation with appropriate metal salts. The steric and electronic properties of the IFcPr ligand were assessed using %Vbur and TEP, respectively. These assessments indicated that the ligand was as bulky as the adamantyl NHC ligand and exhibited strong donor ability similar to that of a triazolylidene NHC ligand. The catalytic performance of the copper and palladium complexes was evaluated in the asymmetric borylation of ethyl cinnamate and Suzuki–Miyaura coupling reactions, respectively. The IFcPr‐Cu complex catalyzed the borylation of ethyl cinnamate with bis(pinacolato) diboron, followed by oxidation to yield the hydroxy ester with 58% yield and 30% ee. In contrast, the IFcPr‐Pd‐PEPPSI complex provided the axial chiral binaphthyl compound with 59% yield and 51% ee at a low catalyst loading (0.1 mol%, TON = 590).

Advancing Heterogeneous Organic Synthesis With Coordination Chemistry-Empowered Single-Atom Catalysts.

For traditional metal complexes, intricate chemistry is required to acquire appropriate ligands for controlling the electron and steric hindrance of metal active centers. Comparatively, the preparation of single-atom catalysts is much easier with more straightforward and effective accesses for the arrangement and control of metal active centers. The presence of coordination atoms or neighboring functional atoms on the supports' surface ensures the stability of metal single-atoms and their interactions with individual metal atoms substantially regulate the performance of metal active centers. Therefore, the collaborative interaction between metal and the surrounding coordination environment enhances the initiation of reaction substrates and the formation and transformation of crucial intermediate compounds, which imparts single-atom catalysts with significant catalytic efficacy, rendering them a valuable framework for investigating the correlation between structure and activity, as well as the reaction mechanism of catalysts in organic reactions. Herein, comprehensive overviews of the coordination interaction for both homogeneous metal complexes and single-atom catalysts in organic reactions are provided. Additionally, reflective conjectures about the advancement of single-atom catalysts in organic synthesis are also proposed to present as a reference for later development.

Ligand-to-Metal Charge Transfer (LMCT) Catalysis: Harnessing Simple Cerium Catalysts for Selective Functionalization of Inert C-H and C-C Bonds.

ConspectusChemists have long pursued harnessing light energy and photoexcitation processes for synthetic transformations. Ligand-to-metal charge transfer (LMCT) in high-valent metal complexes often triggers bond homolysis, generating oxidized ligand-centered radicals and reduced metal centers. While photoinduced oxidative activations can be enabled, this process, typically seen as photochemical decomposition, remains underexplored in catalytic applications. To mitigate decomposition during LMCT excitation, we developed a catalytic cycle integrating in situ coordination, LMCT, and ligand homolysis to activate ligated alcohols transiently into alkoxy radicals. This catalytic approach leverages Ce(IV) LMCT excitation and highly reactive alkoxy radical intermediates for selective functionalizations of C(sp3)-H and C(sp3)-C(sp3) bonds under mild conditions. In this Account, we discuss these advancements, highlighting the practical utility of cost-effective cerium salts as catalysts and their potential to develop innovative transformations, addressing long-standing synthetic challenges.Selective functionalization of chemically inert C(sp3)-H bonds has long posed a significant challenge. We first detail our research using LMCT-enabled alkoxy radical-mediated hydrogen atom transfer (HAT) processes for selective C(sp3)-H functionalizations. Using readily available CeCl3, we established a general protocol for employing free alcohols in the Barton reaction. By integrating LMCT and HAT catalysis, we introduced a selective photocatalytic strategy for functionalizing feedstock alkanes, converting gaseous hydrocarbons into valuable products. Employing simple cerium salts like Ce(OTf)3 and CeCl3, we achieved selective C-H amination of methane and ethane at ambient temperature, achieving turnover numbers of 2900 and 9700, respectively. This catalytic manifold has been further exploited to address the site-selectivity challenge in the C-H functionalization of linear alkanes. The use of methanol as a cocatalyst enabled preferential functionalization of the most electron-rich sites, achieving a high intrinsic selectivity over 12:1 of secondary vs primary sites in pentane and hexane.Next, we discuss the catalytic utilization of alkoxy-radical-mediated β-scission, a frequently encountered side reaction in HAT transformations, for selective cleavage and functionalization of C-C bonds. The versatility of the LMCT catalytic platform facilitates the generation of alkoxy radicals from various free alcohols. In our initial demonstration of LMCT-enabled C(sp3)-C(sp3) bond activation, we developed a cerium-catalyzed ring-opening and amination of cycloalkanols, providing an effective protocol for cleaving unstrained C-C bonds. This strategy has been successfully applied to various radical cross-coupling processes, leading to innovative transformations such as ring expansions of cycloalkanols, dehydroxymethylative alkylation, amination, alkenylation, and ring expansions of cyclic ketones. These results highlight the synthetic potential of employing LMCT-mediated β-scission and ubiquitous C-C bonds as unconventional functional handles for generating molecular complexity.Lastly, we delve into our mechanistic investigations. Beyond the catalytic application of Ce(IV) LMCT in various transformations, we have undertaken comprehensive mechanistic studies. These investigations encompass characterization of Ce(IV) alkoxide complexes to elucidate their structures, evaluation of their photoactivity and selectivity in radical generation, and elucidation of kinetic pathways associated with transient LMCT excited states. Our research has revealed ultrafast bond homolysis, back electron transfer, and the selectivity of heteroleptic complexes in homolysis, providing crucial insights for advancing LMCT catalysis.

Preparation, Characterization, In Vitro Biological Evaluation, DFT Calculations, and Molecular Docking Investigations of 1H-Imidazole-2-Carboxylic acid and Histidine-Based Mixed-Ligand Complexes.

Mixed-ligand complexes incorporating 1H-Imidazole-2-Carboxylic acid (IMCA) and Histidine (LHIS) show promise for biomedical and biotechnological applications. This study synthesizes and characterizes FeIMCALHIS, CoIMCALHIS, and NiIMCALHIS coordination compounds using metal chloride salts (FeCl3.6H2O, CoCl2.6H2O, NiCl2.6H2O) in ethanolic solutions. The complexes are characterized by spectroscopic methods (IR, UV-vis, and mass spectra), elemental analysis, conductivity, magnetic, and thermal analysis. Molar conductivity indicates their non-electrolytic nature. UV-vis spectra reveal absorption bands with pathochromic shifts, and electronic spectra show characteristic metal-ligand transitions, indicating their structural configuration and coordination geometry. 3D geometry optimization shows six-coordination around Fe(III) and Co(II) in FeIMCALHIS and CoIMCALHIS, and four-coordination around Ni(II) in NiIMCALHIS. Analysis of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) suggests decreased electron donation ability upon coordination. Electronic structure parameters (HOMO, LUMO, ionization potential, energy gap, electron affinity, chemical potentials, and electronegativity) provide further insights into stability and reactivity. The metal complexes exhibit enhanced antimicrobial, antioxidant, and anti-inflammatory activity compared to individual ligands, with FeIMCALHIS showing notable antimicrobial activity. Molecular docking analysis reveals strong binding interactions with target proteins, highlighting their potential therapeutic applications.