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γ-Glutamyl-β-cyanoalanylglycine (gEcnAG) is a glutathione analog in which the cysteine moiety in glutathione is replaced with β-cyanoalanine, a known plant cyanide metabolite. Previously, gEcnAG was detected in the liver of rats and chicks exposed to β-cyanoalanine. We reported the detection of gEcnAG in naïve mammalian cells using liquid chromatography coupled with tandem quadrupole time-of-flight mass spectrometry (LC-QTOF-MS). LC-QTOF-MS analysis enabled high-resolution confirmation (exact mass determination and MS/MS fragmentation) of the gEcnAG structure. The detection of gEcnAG in rat pheochromocytoma (PC12) cells that were not exposed to β-cyanoalanine suggests its endogenous production. Furthermore, the inhibition of myeloperoxidase, an enzyme potentially required for endogenous cyanide generation, decreased gEcnAG levels in PC12 cells. This supports the notion that PC12 cells intrinsically produce cyanide, unlike HepG2 cells, which exhibited lower intracellular gEcnAG levels. Notably, β-cyanoalanine was undetectable in PC12 cells. Moreover, depleting glutathione with buthionine sulfoximine reduced intracellular gEcnAG levels, whereas supplementation with glutathione reduced ethyl ester increased them. These observations suggest that endogenous gEcnAG may be generated from glutathione, potentially through its reaction with endogenous cyanide. Our findings implicate gEcnAG as a possible metabolite of endogenous cyanide. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: The first asymmetric hydrogenation of acyclic tetrasubstituted α,β‐unsaturated amides has been achieved by using Rh/DuanPhos complex as a catalyst, delivering chiral β‐amino amides with two contiguous chiral centers in excellent yields and high enantioselectivities (up to 99% yield, 96% ee), which provides efficient and concise access to valuable β‐amino amide derivatives. The gram‐scale reaction and efficient transformation of β‐amino amide to β‐amino acid and β‐amino cyanide demonstrated the utility of this methodology. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: The first asymmetric hydrogenation of acyclic tetrasubstituted α,β‐unsaturated amides has been achieved by using Rh/DuanPhos complex as a catalyst, delivering chiral β‐amino amides with two contiguous chiral centers in excellent yields and high enantioselectivities (up to 99% yield, 96% ee), which provides efficient and concise access to valuable β‐amino amide derivatives. The gram‐scale reaction and efficient transformation of β‐amino amide to β‐amino acid and β‐amino cyanide demonstrated the utility of this methodology. [ABSTRACT FROM AUTHOR]

N1‐substituted derivatives of anti‐(2R,3S)‐1,3‐diamino‐4‐phenylbutan‐2‐ol are important building blocks for the synthesis of therapeutically important molecules. We describe a simple protocol that allows transformation of N,N‐dibenzyl‐L‐phenylalaninal into such compounds in only two steps. The first step is a fully stereoselective three‐component MAC (Masked Acyl Cyanide) oxyhomologation reaction implicating different amines to give a panel of ten N,N‐dibenzyl‐O‐tert‐butyldimethylsilyl‐protected anti‐(2S,3S)‐allophenylnorstatin amides. The second step is a carbonyl‐activated hydride deprotection/reduction protocol using trimethylsilyl chloride and lithium aluminium hydride; the one‐pot two‐component system is more efficient than the alternative approach of isolating the deprotected amide intermediate before reduction. [ABSTRACT FROM AUTHOR]

A series of D‐π‐A alkynylphosphonium salts with different linker between donor and acceptor groups was used to synthesize two series of trans‐bis‐alkynylphosphonium Pt(II) complexes with different ancillary ligands (triphenylphosphine, P series, and cyanide, CN series). The nature of the ancillary ligand manages the overall charge and emission properties of the complexes obtained. In addition, the variation of the linker in alkynylphosphonium ligands allows fine‐tuning the luminescence wavelength. Dicationic series P is unstable in solution under UV excitation, whereas in the solid state, these complexes are the first example of phosphorescent trans‐phosphine‐bis‐alkynyl Pt(II) compounds. Neutral series CN demonstrates bright emission in solution, including dual emission for 2CN complex with biphenyl linker in alkynylphosphonium ligand. However, in the solid state for the CN series drastic decrease in the emission quantum yield compared to the P series was observed. DFT calculations reveal the complicated emission nature for the both P and CN series with various contributions of 3ILCT, 3LLCT and 3MLCT states. However, in the naphthyl‐containing derivatives 3P and 3CN, the dominating 3LC character with some admixture of CT states is postulated. [ABSTRACT FROM AUTHOR]

AbstractImidazole, a five-membered heterocyclic compound, has multipurpose applications for its bioactivity, uses in charge transport materials, and NLO materials. The review provides a comprehensive survey of the synthetic strategies of imidazole from various starting materials, highlighting their percentage yield and mechanistic insights. The most popular starting materials for the syntheses of imidazole include diketones, cyanides, imines, amidines, imidamides, di-amines, and oximes. Although the selection of a particular synthetic strategy will depend largely on the desired imidazole derivative, the survey consists of more than a century of research on imidazole synthetic procedures, starting with Heinrich Debus synthesis in 1858 till the present day. Most recent advancements and future perspectives in the field have been explored. The study will help researchers choose the most suitable starting material, catalyst, solvent, or reaction conditions for the synthesis of various imidazole derivatives. [ABSTRACT FROM AUTHOR]

The direct addition of a nitrile anion to isocyanates is reported for a straightforward preparation of valuable cyanoformamides. Through the proper activation of an adequate silicon‐ate complex precursor (PhMe2SiCN) with a Lewis base (potassium tert‐amylate) under Barbier‐type conditions, the cyanide was instantaneously released, thus yielding the desired motif with full chemocontrol. No particular structural restriction was noticed for engaging in the transformation a wide series of commercially available isocyanates. [ABSTRACT FROM AUTHOR]

Biological treatment processes at low or neutral pH are ineffective for gold mine wastewater treatment. The aim of this study was to develop a new cyanide-rich gold mine wastewater treatment system using alkaliphilic microbial consortia from the Ethiopian Rift Valley soda lake, Lake Chitu. The treatment setup incorporates aerobic and anoxic reactors connected in series and operated for about 200 treatment days. Simulated gold mine wastewater was formulated in the laboratory. Colorimetry was used to measure residual cyanide and reactive nitrogen molecules derived from cyanide biodegradation. Flocks and biofilms developed in the reactors during the acclimatization process. Using sodium cyanide at 200 mg/L as an initial concentration, the consortia degraded to 99.74 ± 0.08% of cyanide, with no significant variation (p > 0.05) occurring when the dose was increased to 800 mg/L. However, changes were observed (p < 0.05) at 1000 mg/L. Acetate was the preferred carbon source for the consortia. The established consortia effectively degraded cyanide to levels below the permissible discharge limit set by the International Cyanide Management Institute (ICMI). This study provides insights into the effectiveness of alkaliphilic microbial consortia derived from soda lakes for treating cyanide-polluted wastewater. [ABSTRACT FROM AUTHOR]

An alternative biomarker for assessing the cyanide levels in postmortem materials is crucial for investigating acute cyanide intoxication. Herein, an aptamer–ligand biorecognition system with high specificity was developed to detect acute cyanide poisoning via its secondary metabolite, 2-amino-2-thiazoline-4-carboxylic acid (ATCA). Potential aptamers were screened from a random library of 66-base single-stranded DNA using GO-SELEX, with individual aptamers being identified through single-stranded DNA sequencing. Molecular docking was employed to predict the affinity of these aptamers toward ATCA and selected counter-targets; these predictions were confirmed using thermodynamic analysis with an isothermal titration calorimeter. Owing to its label-free biomolecular binding interactions, Apt46 exhibited the highest affinity against ATCA and notable selectivity against structurally similar counter-targets. Thus, an amino-tagged Apt46 binding aptamer was attached to a carbon electrode modified with EDC–NHS-activated graphene oxide. The binding of Apt46 to ATCA was quantified by measuring current changes using differential pulse voltammetry. The aptasensor achieved a detection limit of 0.05 µg/mL and demonstrated suitability for detecting ATCA across various biological matrices, with the high recovery percentages ranging from 92.29 to 114.22%. Overall, the proposed ATCA aptasensor is promising for identifying ATCA metabolites in cases of acute cyanide exposure. [ABSTRACT FROM AUTHOR]

The main chemical, ecotoxicological, and environmental fate characteristics of cyanide, along with its treatment methods for cyanide-contaminated wastewater, were thoroughly examined. A global biogeochemical cycle of cyanide is proposed, covering the key physicochemical processes occurring in aqueous, soil, and atmospheric environments. The principles, advantages, and disadvantages of various treatment methods—including chemical, physicochemical, electrochemical, photochemical, and biological approaches—are evaluated. Finally, the feasibility of reusing cyanide waste is explored. [ABSTRACT FROM AUTHOR]

The article discusses the recent awards given by the Chemistry Education Group at their annual conference. Prof. Dr. Klemens Koch received the Manfred-und-Wolfgang-Flad Prize for his outstanding experimental presentations and contributions to chemistry education. StD Jürgen Nikolaus Kopp was awarded the Heinrich-Roessler Prize for his dedication to teaching and his efforts in environmental education. Evelin Mietschke received the Friedrich-Stromeyer Prize for her long-standing commitment to chemistry education and her success in mentoring students in various competitions. Additionally, two members of the group, Dr. Christa Jansen and Prof. Dr. Gisela Lück, were honored with honorary memberships for their exceptional contributions to chemical education. The article also includes a checklist for planning science laboratories in schools, emphasizing the importance of maintaining safety standards and providing adequate resources for experimental teaching. [Extracted from the article]

Bacterial persisters avoid antibiotic-mediated death by entering a dormant state and are considered a major cause of antibiotic treatment failure. Antimicrobial peptides (AMPs) with membrane-disrupting activity are promising drugs to eradicate persister cells. In this study, carbonyl cyanide m-chlorophenylhydrazone (CCCP), ciprofloxacin (CIP), and rifampicin (RFP) were applied to induce the formation of multidrug-resistant Pseudomonas aeruginosa (MRPA0108) persisters, and the antibacterial activity and mechanisms of I1W and L12W (two Trp-containing peptides designed in our lab) against MRPA0108 persisters were investigated. The results showed that I1W and L12W displayed potent antibacterial activity against MRPA0108 persisters. Both Trp-containing peptides disturbed the inner and outer membrane of MRPA0108 persisters. In addition, I1W and L12W revealed novel antibacterial mechanisms by decreasing the enzymatic activities of superoxide dismutase (SOD) and catalase (CAT), increasing reactive oxygen species (ROS) and malondialdehyde (MDA) levels, consequently leading to oxidative stress. The transcriptome profile of I1W-treated MRPA0108 persisters revealed that the genes involved in carbon metabolism, biosynthesis of amino acids, and the TCA cycle were downregulated, indicating that I1W interfered with metabolism and energy synthesis processes. Furthermore, both Trp-containing peptides displayed synergistic activities with antibiotic tobramycin and showed additive activities with cefepime or ciprofloxacin, which revealed a potential therapeutic strategy for the eradication of MRPA0108 persisters. [Display omitted] • I1W and L12W, two Trp-containing peptides, exhibited high antibacterial activity against MRPA0108 persisters. • I1W and L12W killed MRPA0108 persisters by disturbing cell membrane and inducing substantial oxidative stress. • I1W and L12W displayed synergistic activities with tobramycin and additive activities with cefepime or ciprofloxacin. [ABSTRACT FROM AUTHOR]

In industrial production, the preparation of cubic boron nitride (cBN) under high temperature and pressure wastes a large amount of unreacted hexagonal boron nitride (hBN). This study aims to use this BN waste (wBN) as a raw material, composite it with g-C3N4 to construct wBN/g-C3N4 composites, and apply the composites in the field of photocatalysis. wBN/g-C3N4 composites were prepared by simple calcination using wBN and ammonium cyanide as raw materials. Results showed that a heterogeneous structure was formed in the composite photocatalyst, with a decrease in its bandgap width and a significant increase in its ability to absorb light. The simulated sunlight photocatalytic activity of composite photocatalysts was significantly better than that of single wBN or g-C3N4. The photocatalytic performance of B2 sample, composed of a 4:3 ratio of wBN and melamine in the raw materials, demonstrated the highest efficiency. Under simulated solar illumination, it was capable of degrading 99.3% of MB within 60 min. The experimental results with additional capture agents indicated that the main reactive species of the composite photocatalyst were superoxide radicals (·O2−) and holes (h+). [ABSTRACT FROM AUTHOR]

Some pharmaceutical ingredients use cyanide in their synthesis, and this impurity must be controlled as per ICH, FDA and EDQM regulatory compliance. Spectrophotometric approaches for measuring cyanide levels are confined to water or water-soluble compounds with poor solution stability and low sensitivity. No method is available for the cyanide in water-insoluble drug substances through spectrophotometry. To address this gap, our study proposed a spectrophotometric approach for measuring trace cyanide in water-insoluble drugs such as Primidone and Clobazam. This method utilizes chloramine-T, which reacts with cyanide to form cyanogen chloride (CNCl), consequently reacting with pyridine-barbituric acid to produce a coloured derivative (C13H10N4O6, MW: 318.06 g/mol). This protocol also involves the selection of a suitable solvent and optimizing the pH for sensitive/accurate quantification of cyanide impurity. Mass spectrometry confirms cyanide derivatization as part of the orthogonal procedure comparison of ICH Q2 (R2). Method validation follows ICH Q2 (R2) guidelines in determining specificity, LOD (0.396 ppm), LOQ (1.200 ppm), linearity (1.2-45 ppm), and recovery (91-99% with %RSD<10%) of the method. The stability of the pyridine-barbituric acid reagent and derivatized compound was also evaluated. This approach effectively measures cyanide in water-insoluble drugs, meeting essential regulatory standards. [ABSTRACT FROM AUTHOR]

A series of selectively cyanated spirofluorene‐bridged N‐heterotriangulenes (N‐HTAs) with three to nine cyano groups are synthesized via a newly developed synthetic strategy. X‐ray crystallographic analysis of the compounds revealed a tripod‐like molecular shape with the fluorenyl moieties arranged in a perpendicular fashion around the nitrogen‐centered N‐HTA core. The solid state packing is found to be strongly influenced by the dipolar cyano functions. Under electrochemical conditions, the N‐HTA core is prone to undergo a reversible one‐electron oxidation toward the nitrogen‐centered radical cation, which becomes increasingly difficult as the number of the cyano acceptors, and consequently the ionization potential, increases. While a clear bathochromic shift is observed in the steady‐state UV–vis absorption spectra, the fluorescence behavior is complex and strongly dependent on the position and number of the cyano groups. The compound with six cyano functions at the fluorenyl flanks is unique within the series and shows a broad emission maximum at 499 nm and an unusually large Stokes shift of 10 171 cm−1. Time‐resolved absorption and fluorescence measurements, supported by quantum chemical calculations, identified this spectroscopic signature to originate from fast and robust photoinduced intramolecular charge transfer. [ABSTRACT FROM AUTHOR]

Cyanate, a toxic product from the chemical oxidation treatment of highly toxic cyanide, can be converted to harmless ammonia and carbon dioxide by cyanase (EC 4.2.1.104). Cyanase from Thermomyces lanuginosus was entrapped in biomimetic silica to improve stability and reusability. After entrapment, the enzyme's activity increased by two-fold, and the residual activity after 30-min of incubation at 60 °C also increased by two-fold, compared to the free enzyme. After being stored at room temperature for 28 days, the entrapped cyanase retained 79% of the initial activity, while the free form retained 61%. The immobilized cyanase was successfully applied to cyanate detoxification; the co-entrapment of carbonic anhydrase from Sulfurihydrogenibium azorense decreased the amount of bicarbonate necessary for cyanate detoxification by 50%. The cyanate degradation retained 53% of the initial value after the co-entrapped cyanate and carbonic anhydrase were reused five times. [ABSTRACT FROM AUTHOR]

The synthesis of a (phosphino)(stannyl)carbene is documented. The combination of phosphino and stannyl substituents imparts a highly ambiphilic nature to this carbene, enabling reactions with cyanide, isocyanide, and carbon monoxide. This leads to rare stannylketenimines and a stannylketene. [ABSTRACT FROM AUTHOR]

We present a practical and convergent synthesis of glycoalkaloids solasonine 1 and its saponin derivative 2, incorporating a {3-O-α- L -rhamnopyranosyl-(1→2)-O-[β- D -glucopyranosyl-(1→3)]-β- D -galactopyranoside} moiety. The key features of this strategy include the following: (1) AuCl3–tBuCN cooperative catalysis enabling 1,2-trans stereoselective glycosidation of 2-branched trisaccharide trichloroacetimidate donors with steroidal aglycons, in the absence of neighboring group participation; (2) "cyanide effect" mediated regioselective benzoylation of the 4- and 6-hydroxyl groups of galactopyranosyl disaccharide; and (3) an effective approach to prevent orthoester byproduct formation. [ABSTRACT FROM AUTHOR]

A general Pd-catalyzed approach for the conversion of phenols into benzonitriles via aryl imidazolylsulfonates with a non-toxic cyanide source, potassium ferrocyanide, has been developed. Salient features of this method include low palladium precatalyst loadings (as low as 1.0 mol% total Pd), mild reaction conditions, and environmentally benign by-products compared to other (pseudo)halide aryl electrophiles. The initial scope of the reaction on a range of phenolic precursors is demonstrated including a one-pot, two-step approach to convert phenols directly into benzonitriles. [ABSTRACT FROM AUTHOR]

This study aimed to assess the feasibility of employing indigenous cyanide-degrading bacterial strains for the treatment of cassava mill effluent (CME) in Nigeria, a hazardous waste material posing significant public health risks. The physicochemical properties and heavy metal concentrations in CME were determined through standard methodologies. Cyanide-degrading bacteria were isolated, characterized, and identified using molecular techniques. These strains were immobilized within a porous network of cross-linked biochar, confirmed through SEM imaging, and evaluated alongside free cells for CME bioremediation. Multiple variables were examined to assess the effluent's pollution load, including pH, electrical conductivity (EC), chemical oxygen demand (COD), biochemical oxygen demand (BOD5), total dissolved solids (TDS), nitrate (NO3), phosphate (PO4), and cyanide levels, falling within respective ranges of (4.00-4.02), (2394-2618 S/cm), (985-1219 mg/L), (1556-1667 mg/L), (3459-3705 mg/L), (2709-2812 mg/L), (251-311 mg/L), (87.25-118 mg/L), and (25.00-28 mg/L). Copper was the most prevalent heavy metal in the effluent, while chromium was detected at the lowest levels, with mean values of 10.00-12.39 mg/L and 0.00-0.27 mg/L, respectively. The study revealed severe contamination of the effluent, above the Federal Environmental Protection Agency (FEPA) threshold limit. The 16S rDNA of the cyanide degrading bacteria were deposited at the NCBI database and the following GenBank accession numbers were assigned (MK71248O, MK71281, MK712482, and MK712483) for Pseudomonas putida, Bacillus subtilis, Alcaligenes faecalis and Leuconostoc mesenteroides respectively. Results of the bioremediation approach demonstrated a substantial reduction in physicochemical parameters and heavy metal contents, indicating a promising biological treatment strategy to mitigate CME's adverse effects on public health. In conclusion, despite elevated physicochemical parameters and heavy metal concentrations in CME, this study offers a promising avenue for employing biological treatments to mitigate environmental and public health impacts. Further research and application of this technique hold substantial potential for cassava mill effluent management in Nigeria and other regions facing similar challenges. [ABSTRACT FROM AUTHOR]

This paper scrutinises the development of low-cost hypersensitive fluorescent probes manipulated chemically with Schiff base complexes and their prospective applicability for the detection of nitro explosives in light of the rapidly expanding demand for anti-trafficking measures. In this study, a new Zn(II) metal complex has been synthesized in one pot using the Schiff base ligand L= 2-methoxy-5-methyl-N-(2-pyridin-2-ylmethylene) aniline. The complex was also thoroughly characterised using various spectroscopic tools and subjected to single crystal XRD analysis. In the asymmetric unit, square pyramidal zinc (II) centre exist in the inner N2O compartment of the ligand L. The intermolecular Cg···Cg interactions exist between two different asymmetric residual units lead to supramolecular assembly along b axis. By turning off the fluorescence response, the complex serves as a sensor for the detection of nitro aromatics in CH3CN solution. A significant quenching efficiency has been reported with a quenching constant (KSV) 1.8 × 104 M-1 for 4-nitrobenzoic acid during investigation of sensing phenomenon in solution phase. In addition, determining the binding stoichiometry of the chemosensor with NO2 and the binding constant, the mechanism of fluorescence quenching has also been postulated. The detection limit of NO2 is 7.6×10 -7 M, with the binding constant k = 1.1021× 108 M-1. Additionally, the DFT calculation makes it easier to comprehend the appropriate binding process in light of the findings of experiments. We also designed a paper sensor strip for the visual detection of Nitro Explosive Residues in light of the sensor's potential used in forensic investigations. [ABSTRACT FROM AUTHOR]

In recent years, there is an increasing interest in finding better and more efficient ways to detect CN− ions. Most of the anthraquinone-based probes show less fluorescence This paper presents the design and synthesis of a new anthraquinone based imine probe with good colorimetric sensing property and fluorescent turn on behavior toward CN− ion. Herein, we report a receptor with both colorimetric and fluorescent enhancement of cyanide ion in DMSO medium is synthesized. The synthesized receptor shows an immediate color change from orange to pink when cyanide is added; and it can be readily observed visually due to the presence of diverse p-conjugated systems in the receptor. These studies were confirmed by UV–Visible, PL studies, DFT, HRMS and 1H NMR titration. Moreover, this receptor shows 1:1 stoichiometry and micromolar detection limit. Further the receptor was applied to a real sample in finger millet (Eleusine Coracana) to detect the presence of cyanide ion. Moreover, the receptor is applicable toward INHIBITION, IMPLICATION logic gates with two input systems. [ABSTRACT FROM AUTHOR]

The activation of C—C bonds by transition‐metal complexes is of continuing interest and acetonitrile (MeCN) has attracted attention as a cyanide source with comparatively low toxicity for organic cyanation reactions. A diiron end‐on μ‐η1:η1‐CN‐bridged complex was obtained from a crystallization experiment of an open‐chain iron–NHC complex, namely, μ‐cyanido‐κ2C:N‐bis{[(acetonitrile‐κN)[3,3′‐bis(pyridin‐2‐yl)‐1,1′‐(methylidene)bis(benzimidazol‐2‐ylidene)]iron(II)} tris(hexafluorophosphate), [Fe2(CN)(C2H3N)2(C25H18N6)2](PF6)3. The cyanide appears to originate from the MeCN solvent by C—C bond cleavage or through carbon–hydrogen oxidation. [ABSTRACT FROM AUTHOR]

We have already proven that thiazolylketol acetates, synthetised by addition of 2-lithiothiazole to sugar lactones followed by acetylation, are efficient glycosyl donors in the presence of O-, N-, and P-nucleophiles. We describe here their first use in the C-glycosidation using trimetylsilyl cyanide as the acceptor in order to prepare, after thiazole-to-formyl unmasking and reduction, the corresponding C-ketosides. [ABSTRACT FROM AUTHOR]

Certain cyanide leaching tailings in Guizhou contain 1.66 g/t of gold, primarily existing in the forms of exposed gold and sulfide-encapsulated gold. The tailings have a high fineness, with particles of 0.038 mm accounting for over 80%. Given the high slime content of the cyanidation tailings, a sand-slime separation process was employed. Cyclones are used for grading and flotation is performed for the recovery of the underflow and overflow separately. A closed-circuit test with roughing once, scavenging twice, and cleaning three times was conducted, with process parameters and reagent regimes tailored to the characteristics of the underflow and overflow. The sand-slime separation process achieved a concentrate with a gold grade of 12.42 g/t and a gold recovery rate of 50.13%, while the ungraded flotation process of the cyanidation tailings produced a gold concentrate with a grade of 9.49 g/t and a recovery rate of 38. 10%. The results indicate that the sand-slime separation process improved the gold grade by approximately 2.9 g/t and the gold recovery rate by about 12 percentage points, effectively recovering gold from the cyanidation tailings. [ABSTRACT FROM AUTHOR]

New cyanide-bridged heteronuclear compounds, [Cd(NH3)(μ-ampy)M(μ-CN)4]n [ampy = 3-aminomethylpyridine, M: Pd(II) or Pt(II) (hereafter abbreviated as Cd-M-ampy)] have been prepared in powder form and investigated by utilizing elemental analysis, vibrational (FT-IR and Raman) spectroscopy, and thermal analysis. In our previous work, we synthesized the [Cd(NH3)(μ-ampy)Ni(μ-CN)4]n compound and determined its crystal structure. The results of thermal analysis and vibrational spectroscopic show that the structural characteristics of Cd–Ni-ampy and Cd–M-ampy [M: Pd(II) or Pt(II)] compounds are analogous to each other. In these compounds, while the sphere of the center of the M(II) ion has a square pyramidal geometry, the coordination sphere of the Cd(II) ion is identified to have a distorted octahedral geometry. While one amine, one ampy, and four cyanide ligands coordinate to the Cd(II) ion, a three-dimensional coordination polymer forms by the coordination of these ligands to the Cd(II) and M(II) ions. Thermal degradation of the compounds occurs in two steps: degradation of ampy and amine ligands and release of the cyanide groups. [ABSTRACT FROM AUTHOR]

Gold extraction has long relied on cyanidation yet faces challenges including toxicity and refractory ore usage. This study explores the glycine-copper-cyanide leaching system's potential for gold recovery from sedimentary rock-hosted disseminated Agh-Darreh gold ore. Initially, cyanidation experiments tested increasing temperatures' impact. Concurrently, classical experiments evaluated key parameters—temperature, time, and sodium cyanide to copper cyanide molar ratio—on gold leaching with glycine. Design of Experiments (DOE) methodology was applied, considering three interaction parameters. Results showed 90% recovery at 50°C, peaking at 93% at 35°C with an 8-h leaching time using the glycine-copper-cyanide system. Increasing the sodium cyanide-to-copper cyanide ratio furthered better gold recovery, attributed to copper glycinate complex formation with glycine, enabling free cyanide redistribution. This study underscores the glycine-copper-cyanide leaching system's efficacy as a cyanidation alternative for efficient gold extraction from sedimentary deposits. [ABSTRACT FROM AUTHOR]

• Separable polymers are formed from organic contaminants in raw coking wastewater. • Simultaneous abatement and recovery of organics from coking wastewater is realized. • About 89% of PDS is saved compared to conventional degradation-based process. • Polymerization mechanism is probed by the molecular structure of organic-polymers. • More energy efficient compared to degradation-based processes. Industrial wastewater should be treated with caution due to its potential environmental risks. In this study, a polymerization-based cathode/Fe3+/peroxydisulfate (PDS) process was employed for the first time to treat a raw coking wastewater, which can achieve simultaneous organics abatement and recovery by converting organic contaminants into separable solid organic-polymers. The results confirm that several dominant organic contaminants in coking wastewater such as phenol, cresols, quinoline and indole can be induced to polymerize by self-coupling or cross-coupling. The total chemical oxygen demand (COD) abatement from coking wastewater is 46.8% and the separable organic-polymer formed from organic contaminants accounts for 62.8% of the abated COD. Dissolved organic carbon (DOC) abatement of 41.9% is achieved with about 89% less PDS consumption than conventional degradation-based process. Operating conditions such as PDS concentration, Fe3+ concentration and current density can affect the COD/DOC abatement and organic-polymer yield by regulating the generation of reactive radicals. ESI-MS result shows that some organic-polymers are substituted by inorganic ions such as Cl–, Br–, I–, NH 4 +, SCN– and CN–, suggesting that these inorganic ions may be involved in the polymerization. The specific consumption of this coking wastewater treatment is 27 kWh/kg COD and 95 kWh/kg DOC. The values are much lower than those of the degradation-based processes in treating the same coking wastewater, and also are lower than those of most processes previously reported for coking wastewater treatment. [Display omitted] [ABSTRACT FROM AUTHOR]

By using dielectric spectroscopy in a broad range of temperatures and frequencies, we have investigated dipolar relaxations, the dc conductivity, and the possible occurrence of polar order in AgCN. The conductivity contributions dominate the dielectric response at elevated temperatures and low frequencies, most likely arising from the mobility of the small silver ions. In addition, we observe the dipolar relaxation dynamics of the dumbbell-shaped CN− ions, whose temperature dependence follows the Arrhenius behavior with a hindering barrier of 0.59 eV (57 kJ/mol). It correlates well with a systematic development of the relaxation dynamics with the cation radius, previously observed in various alkali cyanides. By comparison with the latter, we conclude that AgCN does not exhibit a plastic high-temperature phase with free rotation of the cyanide ions. Instead, our results indicate that a phase with quadrupolar order, revealing dipolar head-to-tail disorder of the CN− ions, exists at elevated temperatures up to the decomposition temperature, which crosses over to long-range polar order of the CN dipole moments below about 475 K. Dipole ordering was also reported for NaCN and KCN, and a comparison with these systems suggests a critical relaxation rate of 105–107 Hz, marking the onset of dipolar order in the cyanides. The detected relaxation dynamics in this order–disorder type polar state points to glasslike freezing below about 195 K of a fraction of non-ordered CN dipoles. [ABSTRACT FROM AUTHOR]

A base-induced synthesis of 2-(4-(2-(phenylthio)ethyl)piperazinyl) acetonitriles by reaction of disulfides, 1-(chloromethyl)-4-aza-1-azonia bicyclo[2.2.2]octane chloride and trimethylsilyl cyanide is reported. The scope of the method is demonstrated with 30 examples. The reaction mechanism research indicates that the three-component reaction would be a SN2 reaction. The products exhibit good activities towards advanced synthesis of aqueous soluble acyl-CoA: cholesterol O-acyltransferase-1 (ACAT-1) inhibitors. Our work is superior as it uses less-odor disulfides as carbon sources and EtOH as solvent in a water and dioxygen insensitive reaction system, followed by a simple purification process. [ABSTRACT FROM AUTHOR]

The trans influence of anionic ligands on the nature of the cobalt–carbon bond in trans-[Co(TIM)RX]+-type complexes (R is a C-bound ligand and TIM is 2,3,9,10-tetramethyl-1,4,8,11-tetraazacyclotetradeca-1,3,8,10-tetraene) was probed through the incorporation of cyanide as the second monoanionic axial ligand (X). Salt metathesis reactions between KCN and the corresponding halide precursors readily generate trans-[Co(TIM)(C(CH2)Ph)(CN)]+ (1), trans-[Co(TIM′′)(C(CH3)C6H4-4-tBu)(CN)]+ (2, TIM′′ is the reduced TIM derivative following the formation of an aza-cobalt-cyclopropane moiety), and trans-[Co(TIM)(CH3)(CN)]+ (3). The molecular structures of 1 and 2 were established via single-crystal X-ray diffraction studies. FT-IR spectroscopy revealed a red-shift in the ν(C≡N) stretching frequency from 1 to 3 to 2. The absorption spectra of 1–3 exhibit d–d bands which are substantially blue-shifted from their halide precursors as a result of the enhanced ligand field imbued by the cyanide. Cyclic voltammograms of 1 and 3 consist of an irreversible Co4+/3+ oxidation and an irreversible Co3+/2+ reduction. In 2, a reversible Co-centered reduction is observed at −1.75 V vs. Fc1+/0. Also reported are the crystal structures of trans-[Co(TIM)(CN)2]PF6 (4), trans-[Co(TIM)(CH3)I]PF6 (5) and trans-[Co(TIM)(CH3)2]PF6 (6). The π-accepting capabilities of the cyanide reduce the dπ(Co)-π*(imine) backdonation in 4, while the solely strong σ-donating nature of the –CH3 ligands in 6 exerts a large trans influence and significantly increases the Co-TIM interactions. [ABSTRACT FROM AUTHOR]

Cyanide leaching technology was studied for low-grade oxidized gold ores in Guangxi Province. The gold grade of the raw ores was 1.32 g/t. The gold leaching rate was 90.91% under the optimal conditions for the following conventional leaching process: using steel forging as the grinding medium, a grinding fineness of −0.074 mm accounting for 92.53%, a stirring speed of 1500 r/min, a pulp leaching concentration of 28.57%, a pH value of 10.5, a temperature of 25 °C, a leaching time of 24 h, and a potassium cyanide consumption of 4 kg/t. A new type of mixed aid-leaching agent (0.6 kg/t) was used, with a dosage of potassium cyanide of 2 kg/t. All else being equal, the gold leaching rate increased by 2.17% to 93.20% after 18 h of aid leaching compared to that of conventional leaching for 28 h. Meanwhile, the amount of potassium cyanide used was reduced by 50%. The aid-leaching agents restored the surface activity of passivated gold particles and depressed the adsorption of gold and its complexes by gangue minerals. This approach could shorten the leaching time and increase the gold leaching rate. [ABSTRACT FROM AUTHOR]

Three new hexacyanometallate(III) complexes, namely {[Cd3(4epy)12Cr2(µ-CN)6(CN)6]∙4H2O}n (1), {[Cd3(4epy)12Fe2(µ-CN)6(CN)6]∙4H2O}n (2) and {[Cd3(4epy)12Co2(µ-CN)6(CN)6]∙4H2O}n (3), were synthesized by using 4-ethylpyridine (4epy) ligand and characterized by spectral (FT-IR and Raman), crystallographic (SC-XRD and PXRD), thermal and elemental analyses techniques. Single crystal studies have shown that heterometallic complexes 1–3 form 3D polymers. Each M ion [M = Cr(III) in 1, Fe(III) in 2 and Co(III) in 3] is coordinated by six carbon atoms from cyanide ligands and adjacent metal ions are bridged by cyanide ligands to generate [Cd6M6(CN)12] clusters. Each Cd(II) ion is coordinated by four nitrogen atoms from 4epy ligands and two nitrogen atoms from cyanide ligands to distorted octahedral coordination geometry. In addition, thermal (TG/DTA) properties of the complexes were investigated. Powder X-ray diffraction (PXRD) patterns of the complexes were recorded to control the phase purities. [ABSTRACT FROM AUTHOR]

Synthesis of coordination compounds using dicyanoargentate, [Ag(CN)2]- as inorganic ligand is an interesting topic in the research area of supramolecular chemistry. Again cyano bridged compound is especially significant due to their remarkable structural diversity. As cyanometalate anions has strong affinity towards transition metal ions and it has been widely used as building blocks for the creation of coordination polymer. Dicyanoargentate anion, [Ag(CN)2]- can behaves as bridging ligandas well as monodentate ligand and discrete anion. This review article mostly highlights the monodentate coordination behavior of dicyanoargentate anion towards 3d-transition metal ion in which the transition metal ion is blocked by different blocking ligands. This review also reveals the formation of different dimensionality complexes through Ag•••Ag interactions when dicyanoargentate anion act as monodentate ligand. [ABSTRACT FROM AUTHOR]

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The co-crystallization of S-(CF3)-dibenzothiophenium ("Umemoto" – abbreviated Ume) cations and polycyanometalates with different coordination geometries yields a large structural variety of supramolecular assemblies. In the case of [Ume+]2[Ni(CN)4]2−·CH2Cl2 all four cyanide groups of the square-planar dianion act as chalcogen bond acceptors whereas the sulfur atoms of the Umemoto cations act as biaxial chalcogen bond donors. For tetrahedral [Zn(CN)4]2− a more complex assembly of four Umemoto cations and two dianions is observed. In the case of [Ume+]3[Fe(CN)6]3−·CH2Cl2 one Umemoto cation even acts as a triaxial chalcogen bond donor whereas only 4 out of the 6 cyanide groups act as chalcogen bond acceptors. For [Ume+]3[W(CN)8]3− a polymeric chain structure is observed in which all Umemoto cations act as biaxial chalcogen bond donors. DFT investigations focus on the physical nature of the chalcogen bonds, encompassing energetic assessments, MEP surface plots, QTAIM, and NBO analysis, shedding light on the nature of chalcogen donor–acceptor interactions. The energetic results evidence that total contributions of chalcogen bonds in different synthons range from −7.6 to −16.3 kcal mol−1, surpassing that of hydrogen bonds that range from −4.9 to −11.8 kcal mol−1. [ABSTRACT FROM AUTHOR]

Ferrocene-substituted carbenes have emerged as attractive, redox-active ligands. However, among the compounds studied to date, ferrocenylated 1,2,4-triazol-5-ylidenes, which are closely related to the archetypal imidazol-2-ylidenes, are still unknown. Here, we demonstrate that the triazolium salt [CHN(Me)NCHN(Fc)]I (2; Fc = ferrocenyl), obtained by alkylation of 4-ferrocenyl-4H-1,2,4-triazole (1) with MeI, reacts selectively with metal alkoxide/hydroxide precursors [(cod)Rh(OMe)]2 and [(IPr)Au(OH)] (cod = cycloocta-1,5-diene, IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) to produce the ferrocene-substituted 1,2,4-triazol-5-ylidene complexes [(cod)RhI{CN(Me)NCHN(Fc)}] and [(IPr)Au{CN(Me)NCHN(Fc)}]I in good yields. The complexes were characterised by NMR and IR spectroscopy, mass spectrometry, cyclic voltammetry, and single-crystal X-ray diffraction analysis. Density function theory (DFT) calculations were used to rationalise the electrochemical behaviour of the carbene complexes and to elucidate the bonding situation in these compounds. An analysis using intrinsic bond orbitals (IBOs) revealed that the 1,2,4-triazol-5-ylidene ligand exerted a strong trans influence and showed a synergistic stabilisation by the negative inductive and positive π-donor effects of the nitrogen atoms adjacent to the carbene carbon atom; these effects were enhanced by conjugation with the CH＝N bond at the exterior, similar to that in imidazol-2-ylidenes. [ABSTRACT FROM AUTHOR]

The first example of a bis(cyaphido) complex, trans‐[Ru(dppe)2(C≡P)2], is described, unequivocally demonstrating the synthetic accessibility and stability of complexes that feature more than one cyaphido ligand. Synthesis is achieved from the precedent cation [Ru(dppe)2(C≡P)]+ via sequential coordination and desilylation of the phosphaalkyne Me3SiC≡P. The heteroleptic analogue trans‐[Ru(dppe)2(C≡N)(C≡P)] is also prepared from the same cation and NaCN; both cyaphido complexes are structurally characterized, enabling the first direct comparison of cyaphide with cyanide, its isoelectronic and isolobal counterpart. This demonstrates an enhanced π‐acidity for −C≡P over −C≡N, while computational studies reveal also a higher π‐donor character for the cyaphido ligand. [ABSTRACT FROM AUTHOR]

This study utilized water-soluble fluorescein isothiocyanate (FITC) to cover graphene loaded gold nanoparticle composites, and the fluorescence of the probe molecule FITC was quenched. Then, by adding cyanide to the system, the strong complexation of cyanide ions (CN-) with gold nanoparticles formed a stable complex Au (CN)3-x, gradually restoring the fluorescence of the probe molecules, thereby achieving rapid detection of cyanide. The pH value of the experimental solution, reaction time, and interfering ions were optimized. The experimental results indicated that the FITC-Au NPs fluorescence probe had a minimum detection limit of 0.036 μmol/L for CN- in the presence of an H2O2 environment. There was a good linear relationship within the 0.05-80 μmol/L concentration range. The high stability and selectivity of FITC-Au NPs probes were utilized to achieve rapid detection of CN- in complex samples. This simple, fast, and economical fluorescence sensing system shows great practical potential in the detection of anions in actual samples. [ABSTRACT FROM AUTHOR]

Biological treatment with a stable activated sludge process, followed by chemical treatment is one of the potential and accepted cyanide remediation processes for coke plant wastewater treatment. Biologically treated coke plant wastewater contains free cyanide above permissible limit. Presently, chemical treatment with NaOCl is being used to attenuate free cyanide below permissible limit in biologically treated water. This process increases the TDS and colour content in discharge water. Ca(OCl)2 can be used as an alternative to NaOCl for cyanide remediation in biologically treated coke plant wastewater without increasing TDS. In the present work, cyanide removal efficiency of NaOCl and Ca(OCl)2 for real coke plant wastewater after biological treatment has been studied. Optimisation of chemical dosage, treatment time and pH study has been done for Ca(OCl)2 and NaOCl treatment. It was found that up to 90% of free cyanide removal could be achieved through Ca(OCl)2 treatment without increasing the TDS value. In addition, more than 50% colour of the wastewater was removed. pH elevation step required in NaOCl treatment can be eliminated in Ca(OCl)2 treatment, thereby reducing caustic consumption. The study indicated that the use of Ca(OCl)2 is economically more viable than that of NaOCl in cyanide treatment. [ABSTRACT FROM AUTHOR]

In recent years, noticeable progress has been made in the development of alternative extraction systems characterized by greater sustainability. In this context, deep eutectic solvents (DESs) have emerged as a promising alternative to the conventional solvents commonly used in metal extraction. This work focuses on investigating the extraction of lanthanum in an aqueous solution of sulfuric acid using a deep eutectic solvent, employing molecular dynamics simulations (MD). The structural characteristics of the solvent and its interactions with the components of the aqueous solution are explored. In this study, tetraethylammonium bromide (TEABr) is combined with ethylene glycol (EG) to form a DES, in which sodium cyanide (NaCN) is subsequently solubilized. According to the results obtained from the MD simulation, the primary interactions in the DESs are established through hydrogen bonds between the bromine and the hydrogens of the methyl group of tetraethylammonium at 3.5 Å, as well as between the bromine and the hydrogens of the methylene group of ethylene glycol at 3.5 Å. Similarly, the main interactions between the binary DES and sodium cyanide occur through the hydrogens of the hydroxyl group of EG and the carbon of cyanide at 1.7 Å, and between the oxygen of the hydroxyl group of EG and the sodium at 2.5 Å. In the acidic solution, the primary interaction is highlighted between the lanthanum ion and the oxygen of the bisulfate at 2.8 Å. Additionally, it is observed that the interaction between the DES and the aqueous solution occurs between the lanthanum and the oxygen of the hydroxyl group of EG, as well as between the lanthanum and the carbon of cyanide at 4.4 Å. It is important to note that, when increasing the temperature from 25 to 80 °C, the interaction distance between the lanthanum and the carbon of cyanide decreases to 2.4 Å, suggesting a possible correlation with the increase in lanthanum extraction, as experimentally observed. Overall, this study underscores the importance of considering the fundamental structural interactions of the DES with the lanthanum acid solution, providing an essential theoretical basis for future experimental investigations. [ABSTRACT FROM AUTHOR]

In thiosulfate leaching of gold, the copper-ammonia complex serves as an oxidant and catalyst. This study examined the impact of magnetizing the copper-ammonia thiosulphate lixiviant solution on gold leaching from refractory oxidized ores. Magnetization reduced surface tension, improved wettability and infiltration, and enhanced the diffusion of leaching agents. It also increased dissolved oxygen content and boosted the catalytic efficiency of copper-ammonia complexes. These changes led to more efficient gold extraction, with column leaching showing a 4.74% improvement in extraction rates compared to non-magnetized methods and a 3.67% improvement over cyanide processes. These findings suggest that magnetized copper-ammonia thiosulphate lixiviant is a promising, environmentally friendly alternative to cyanide for refractory oxidized gold ores. [ABSTRACT FROM AUTHOR]

A concise and direct Brønsted acid catalyzed cyanation of secondary and tertiary benzylic and allylic alcohols has been developed using trimethylsilyl cyanide (TMSCN) as a cyanide source and 1,1,1,3,3,3‐hexafluoro‐2‐propanol (HFIP) as a solvent. The present transition‐metal‐free catalytic process is operationally simple to perform under "open‐flask" conditions and is applicable to the preparation of a number of α‐arylacetonitriles as well as late‐stage material transformations. The effectiveness of the present protocol was further demonstrated by the first enantioselective synthesis and determination of the absolute configuration of verimol F. [ABSTRACT FROM AUTHOR]

Free cyanide (fCN) consisting of HCN and CN- is highly hazardous. Today, removal of cyanide from industrial (mining, plating, coke-plant) wastewaters largely relies on physicochemical processes followed by microbial degradation. Enzymatic processes are gaining ground but are still at a low technological stage. The cyanide-converting enzymes of interest are primarily cyanide dihydratases (CynDs; EC 3.5.5.1.), which hydrolyze HCN to formic acid and ammonia, and cyanide hydratases (CynHs; EC 4.2.1.66), which hydrate HCN to formamide. CynHs usually have much higher specific activities and a broader pH profile especially in the alkaline region compared to CynDs. However, the product of CynH, formamide, although much less toxic than fCN, still poses a significant health risk. Therefore, it is attractive to combine the CynH with an amidase that converts formamide to formic acid and ammonia. Here we demonstrate on a laboratory scale a two-step "one-pot" detoxification of fCN (5 mM) to formic acid using recombinantly produced purified enzymes − CynH from Exidia glandulosa and formamidase (EC 3.5.1.49) from Bacillus cereus. The reaction proceeds at pH 9.0–10.0, which reduces the risk of HCN escape. We also hypothesize that the cascade can be used for fCN determination after coupling an NAD-dependent formate dehydrogenase. [Display omitted] • Cyanide hydratase degrades hydrogen cyanide to formamide which is still toxic. • We combined cyanide hydratase with formamidase to detoxify formamide. • The recombinantly expressed, purified enzymes were used in a one-pot process. • The enzymes were active under alkaline conditions suitable for handling cyanide. • HCN was converted to formate with no significant amount of formamide. [ABSTRACT FROM AUTHOR]

A novel fluorescence chemosensor BDP (2-(1-(benzothiazol-2-yl)-5-(4-(diphenylamino)phenyl)-4,5-dihydro-1H-pyrazol-3-yl)phenol) has been synthesized and its sensing behavior has been screened towards various cations by absorption, emission and mass spectroscopic techniques. The probe BDP detects Cu2+ ions preferentially over other metal ions, and the resulting BDP-Cu2+ ensemble acts as a secondary sensor for cyanide anion detection over other anions. The fluorescence intensity of the probe BDP is quenched when it comes into contact with Cu2+ ions, but it is increased reversibly when it comes into contact with cyanide anion, according to spectroscopic measurements. Along with this, optical studies indicate that the sensor BDP has capability to sense Cu2+ and CN- ions selectively over other examined competitive ions with the LOD of 2.57×10-8 M and 2.98×10-8 M respectively. The detection limit of Cu2+ ions is lower than the WHO recommended Cu2+ ions concentration (31.5 µM) in drinking water. On the basis of "on-off-on" fluorescence change of the probe BDP upon interaction with Cu2+ and CN- ions, a possible mechanism for this selective sensing behavior was presented and IMPLICATION logic gate was successfully designed. Furthermore, cell imaging investigations were used to investigate the probe BDP's biological applicability. [ABSTRACT FROM AUTHOR]

This article explores the use of cyanophosphates as synthetic intermediates in the transformation of benzaldehydes into benzonitriles. The researchers found that certain benzaldehydes reacted with tetrabutylammonium azide to form aromatic nitriles, while ketone or aliphatic aldehyde cyanophosphates resulted in the formation of tetrabutylammonium ethyl phosphates. The study also investigated the effects of reaction conditions on the transformation process. The document provides detailed information on the synthesis and characterization of various cyano(phenyl)methyl diethyl phosphate compounds, including their isolation methods and spectroscopic data. Additionally, the document includes chemical data for other compounds, such as tetrabutylammonium 3-(tert-Butyldimethylsiloxy)-17-cyanoestra-1,3,5(10)-trien-17-yl Ethyl Phosphate and 3-nitrobenzonitrile, along with their synthesis and purification methods. The authors express gratitude to their colleagues for their support and assistance. [Extracted from the article]

It is known that the cracked structure of the particles has positive effects in leaching processes. In this respect, high pressure grinding rolls (HPGR) provides some advantages such as increasing leaching efficiency and reducing leaching time by creating more cracked particles compared to other crushers. Although there are studies on the advantages of HPGR on different ores, these have not been fully demonstrated in low grade gold ores, and leaching kinetics have not been examined in detail in the studies conducted in this context. In this study, first of all, crack formation in a low grade gold ore by crushing with HPGR and jaw crusher was investigated. Then, bottle roll tests were performed in different size fractions and different cyanide concentrations along with column leaching of the pelletized ore in a single test condition. As a result of the studies, it was determined that 2–3 times more cracked particles were formed in HPGR depending on the particle size. It was shown that the modified Kelsall model explains the kinetics better than other kinetic models tested. In summary, it was revealed that maximum gold extractions are almost same for HPGR and jaw crushers. However, the fast dissolution kinetic constant was found to be around 25% higher for HPGR than for the jaw crusher in bottle roll tests while this ratio was approximately 30% higher in column leaching tests, suggesting a distinct influence of the crushing method on the dissolution kinetics. [ABSTRACT FROM AUTHOR]

Two novel isostructural cyanide‐bridged hexadecanuclear complexes with the general formula {[Fe(CN)6]6[M{en(Bn)py}]10}2+ [M=Fe (12+), Ni (22+)] have been synthesized. The structural analyses disclose the presence of multivalent Fe centres with different spin states in complex 12+ whereas all the Fe centres share a conserved oxidation state in complex 22+. The DC magnetic study revealed antiferromagnetic interactions between the adjacent metal centres and ferrimagnetic behaviour in 12+. On the other hand, ferromagnetic interactions were observed in complex 22+ due to nearly orthogonal orientation of the interacting orbitals and poor spatial overlap as observed in BS‐DFT calculations. [ABSTRACT FROM AUTHOR]