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P‐stereogenic phosphines, renowned for their utility as ligands and catalysts, have been instrumental in the field of asymmetric catalysis. However, the catalytic asymmetric synthesis of chiral ligands possessing both axial and phosphine chirality remains a significant challenge. Here, we present the successful demonstration of a Cu‐catalyzed asymmetric C−P construction using in situ generated secondary phosphine and heteroaryl chloride. By introducing a chiral NHC ligand and an achiral diphosphine auxiliary ligand, we effectively alleviated the poisoning effect caused by phosphine(III) compounds and suppressed the nonenantioselective background reaction. The reaction exhibited excellent enantioselectivity, with up to 96 % ee, and good diastereoselectivity, with up to 14 : 1 dr, when employing less sterically hindered secondary phosphines. This particular substrate poses a significant challenge due to its strong poisoning effect in copper catalysis. [ABSTRACT FROM AUTHOR]

Chiral 2‐azetines and allenes are highly valuable structural units in natural products and useful chemicals. However, enantioselective synthesis of both 2‐azetines and allenes has been extremely challenging. Herein, we present asymmetric construction of chiral 2‐azetines (70–98 % yields and up to 96 % ee) through chiral phosphine‐catalyzed [2+2] annulation of yne‐enones with sulfamate‐derived cyclic imines. These 2‐azetines were easily transformed into chiral allenes upon treatment with Et3SiH, BF3 ⋅ Et2O and water at rt for 2 minutes. Based on the above transformations, a concise one‐pot synthetic procedure combining [2+2] annulation of yne‐enones and sulfamate‐derived cyclic imines under phosphine catalysis and sequential reduction/isomerization/ring‐opening reaction through Et3SiH, BF3 ⋅ Et2O and water was thus set up, providing axially chiral tetrasubstituted allenes in satisfactory yields and enantioselectivities (56–90 % yields and up to 91 % ee). [ABSTRACT FROM AUTHOR]

A stable dialkylphosphinyl radical reacted with bromoboranes to afford the corresponding phosphinoboranes accompanied with a bromophosphine under neutral condition at room temperature. The obtained phosphinoboranes have almost planar structures and have an effective P–B dative π-bond. The formation of phosphinoboranes would proceed via coordination-induced bromine abstraction from bromoboranes as a pivotal step, which was supported by the computational study. [ABSTRACT FROM AUTHOR]

Nucleophilic phosphine-catalyzed annulations are recognized as practical and powerful tools for synthesizing various cyclic compounds. Phosphine acceptors play a key role in nucleophilic phosphine catalysis. The design and synthesis of new phosphine acceptors that are able to introduce new zwitterionic intermediates with new reactivities into phosphine-catalyzed annulations is highly desirable. We recently applied proton-shift principles in the design of new phosphine acceptors, and we synthesized several new acceptors. With the use of these acceptors, we have developed several novel phosphine-catalyzed annulation reactions. In this account, we present a brief introduction to the design and application of a series of acidic-hydrogen-tethered electron-deficient acceptors for phosphine-catalyzed annulation reactions, categorized according to the type of atom (N–H, O–H, C–H) to which the acidic hydrogen is bound. 1 Introduction 2 Phosphine Acceptors Tethered with an Acidic N–H Group 3 Phosphine Acceptors Tethered with an Acidic O–H Group 4 Phosphine Acceptors Tethered with an Acidic C–H Group 5 Conclusions [ABSTRACT FROM AUTHOR]

Self‐assembled peptides are used for diverse applications in the biomedical and technological fields. The morphology and function of the assembled systems are dictated by the peptide sequence and length. In this work, a supramolecular catalyst was obtained upon self‐assembly of the diphenylalanine peptide conjugated to a triphenylphosphine Au(I) complex in acetonitrile. The assembled molecules were characterized by spectroscopic techniques and by scanning electron microscopy. The activity of the catalyst was tested on two substrates in cyclization reactions. The morphology and the dimensions of the assembled systems vary depending on the presence of a carboxyl versus an amide C‐terminal end. The catalyst efficiently promotes intramolecular cyclization reactions. Results obtained encourage the use of self‐assembled peptides for the obtainment of new and efficient catalysts. [ABSTRACT FROM AUTHOR]

Seawater electrolysis is an economical hydrogen production method that necessitates corrosion-resistant and active catalysts. Non-noble metal-based high-entropy compounds emerge as promising catalysts for seawater electrolysis due to their ability to enhance stability and activity via compositional control and tuning. In this investigation, a high-entropy precursor with a fusiform microstructure was utilized to synthesize high-entropy phosphide (HEP) (FeCoNiMnCu)P x and high-entropy oxide (HEO) (FeCoNiMnCu)O x. It is found that phosphorization and oxidization transformed the morphologies of the (FeCoNiMnCu)P x and (FeCoNiMnCu)O x into a layered sphere-shaped microstructure. The unique morphology, high surface area and special hysteretic diffusion effect of high-entropy materials contributed to the exceptional performance of both (FeCoNiMnCu)P x and (FeCoNiMnCu)O x in hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), respectively. Remarkably, both catalysts exhibited excellent stability, running continuously for 160 h at current densities exceeding 100 mA cm−2, which offered the potential for efficient seawater electrolysis. [Display omitted] • (FeCoNiMnCu)P x and (FeCoNiMnCu)O x with layered sphere-shape structure are obtained. • Morphology remodeling from high entropy precursor to target catalysts are analyzed. • The rational nanosheet structure is found to improve stability of hydrogen production. • The catalysts maintain stability over 160 h at a current density exceeding 100 mA cm−2. [ABSTRACT FROM AUTHOR]

In order to mitigate the release of toxic phosphine from aluminum hypophosphite in twin-screw processing, montmorillonite–melamine cyanurate was prepared by three methods: (1) mechanical intercalation, (2) water intercalation and (3) in situ intercalation. The sheet spacing of montmorillonite was increased from 1.140 nm to 1.141 nm, 1.208 nm and 1.217 nm for these three methods, respectively, and scanning electron microscope (SEM) and transmission electron microscopy (TEM) proved that melamine cyanurate was successfully inserted into the montmorillonite sheets. The montmorillonite–melamine cyanurate from in situ intercalation can best inhibit the release of PH3 from aluminum hypophosphite, and the peaks of phosphine, mean values of phosphine and integral of phosphine were reduced by 81.9%, 72.1% and 72.2%, respectively. The mode of action of montmorillonite–melamine cyanuric inhibition of the emission of phosphine from aluminum hypophosphite can be attributed to the physical absorption of montmorillonite and the chemical bonding of melamine cyanurate. In addition, in situ intercalation can slightly improve flame retardancy, attributed to incomplete exfoliation of montmorillonite sheets. [ABSTRACT FROM AUTHOR]

Currently, developing efficient and cost-effective electrocatalysts for hydrogen evolution reaction (HER) is an enormously grand challenge. Herein, an N-doped carbon-encapsulated CoNiP (CoNiP-NC) is successfully prepared using a dual-chelate (ZIF-67@EDTA-Ni2+) precursor by a simple method. Benefiting from the synergistic effects among the redistributed charges, the rich porous structure, and the different chemical states of doped N in the CoNiP-NC, the optimized CoNiP-NC-600 shows an excellent electrocatalytic performance toward HER with an overpotential of 104.2 mV and a small Tafel slope of 71.4 mV/dec to derive a current density of 10 mA/cm2 in 0.5 M H 2 SO 4 solution. Moreover, due to the N-doped carbon shell protection, CoNiP-NC-600 exhibits considerably enhanced stability under the harsh conditions of a 60-h reaction. Density functional theory (DFT) calculations reveal that the optimized CoNiP-NC-600 not only enhances the adsorption of H 2 O but also decreases the desorption of formed H 2 , essentially promoting the catalytic activity. It is believed that our developed method provides an effective and feasible route for constructing bimetallic phosphide electrocatalysts for hydrogen production. [Display omitted] • N-doped carbon-encapsulated CoNiP (CoNiP-NC) is prepared using dual chelates. • CoNiP-NC exhibits excellent HER performance in 0.5 M H 2 SO 4 solution. • Optimized CoNiP-NC needs a small overpotential of 104.2 mV to derive 10 mA/cm2. [ABSTRACT FROM AUTHOR]

While remarkable progress has been made in the development of peptide medicines, many problems related to peptide synthesis remain unresolved. Previously, we reported electrochemical peptide synthesis using a phosphine as a potentially recyclable coupling reagent. However, there was room for improvement from the point of view of reaction efficiency, especially in the carboxylic acid activation step and the peptide bond formation step. To overcome these challenges, we searched for the optimal phosphine. Among phosphines with various electronic properties, we found that electron‐rich triaryl phosphines improved the reaction efficiency. Consequently, we successfully performed electrochemical peptide synthesis on sterically hindered and valuable amino acids. We also synthesized oligopeptides that were challenging with our previous method. Finally, we examined the effect of substituents on the phosphine cations, and gained some insights into reactivity, which will aid researchers designing reactions involving phosphine cations. [ABSTRACT FROM AUTHOR]

In this work, we unveil a novel synthesis of bench stable Ni (II) complexes supported by tetradentate Schiff‐base ligands and the complexes were devoid of any phosphine or phosphine‐based ligand. These Ni‐complexes were successfully applied for the dehydrogenation of secondary alcohols for ketone and ketazine syntheses. Secondary alcohols with different functional groups were well tolerated during catalytic cycle. Moreover, we successfully extended this protocol for the synthesis of biologically significant ketones and ketazines. On the basis of various control experiments, probable reaction pathway was proposed, and an acceptorless alcohol dehydrogenation mechanism was suggested. [ABSTRACT FROM AUTHOR]

We have developed a phosphine catalyzed asymmetric [3+2] cyclization of 3-oxetanone derived MBH carbonates with activated methyleneoxindole, to construct oxetane dispirooxindole skeletons. Diastereodivergent synthesis was realized via the control of the phosphine catalyst. The (−)-DIOP provides the syn diastereoisomers, while the spiro phosphine (R)-SITCP achieves the anti-epimers. [ABSTRACT FROM AUTHOR]

Simple Summary: This study explores the prevalence of phosphine resistance in stored-grain insects. The research, conducted in Greece, examined 53 key insect species and used two assessment protocols, namely, dose–response and CORESTA, to estimate phosphine resistance. The results showed that 13.3% of field populations were resistant, and mortality rates increased with higher phosphine concentrations. According to the dose–response protocol, 37.7% of field populations were found to be resistant, while all populations were susceptible according to the CORESTA protocol. The observed resistance patterns differ from those reported in other regions. The study emphasizes the importance of tailored fumigation strategies considering insect species' susceptibility to phosphine and recommends best management practices and rotational strategies to develop effective resistance management plans. The results offer valuable insights into the dynamic landscape of phosphine resistance in stored-product insects and suggest potential avenues for further research and control measures. Post-harvest losses due to insect infestation and spoilage by bacteria and molds pose significant challenges to global cereal production. This study investigates the prevalence of resistance to phosphine, a commonly used grain protection agent, in stored-grain insects. The research, conducted in various storage facilities across Greece, examined 53 populations of key stored-product insect species. Two assessment protocols, namely, dose–response (at 50–1000 ppm for 3 days exposure) and CORESTA (at 300 ppm for 6 days), were used herein to estimate phosphine resistance. The results showed that 13.3% of field populations were resistant, and mortality rates increased with higher phosphine concentrations. Specifically, according to the dose–response protocol, among the 53 field populations, 37.7% were found to be resistant to phosphine, namely, two populations of O. surinamensis, one of S. oryzae, seven of T. confusum, one of C. ferrugineus, one of T. castaneum, and all populations of R. dominica, whereas, according to the CORESTA protocol, all populations were found to be susceptible to phosphine. The observed resistance patterns differ from those reported in other regions of the world. The study highlights the importance of tailored fumigation strategies, considering insect species varying susceptibility to phosphine. It recommends the use of best management practices and rotational strategies, such as combining phosphine with other methods, to develop effective resistance management plans. The results provide valuable insights into the dynamic landscape of phosphine resistance in stored-product insects and suggest potential avenues for further research and control measures. [ABSTRACT FROM AUTHOR]

Background/Objectives: The mechanisms of action of phosphine are diverse and include neurotoxicity, metabolic inhibition, and oxidative stress; however, its efficacy at low temperatures is unclear. Methods: Comparative metabolomics is suitable for investigating the response of the spotted-wing fly Drosophila suzukii to exposure toward a combination of cold stimuli and fumigant PH3. Results: Under this combined exposure, 52 metabolites exhibiting significant differences in stress were identified and their physiological roles were analyzed in the Drosophila metabolic pathway. Most metabolites were involved in amino acids, TCA cycle, and nucleic acids. In addition, the alteration levels of cell membrane lipids, such as glycerophospholipids, sphingolipids, and glycerolipids, clearly showed changes in the combined treatment compared to PH3 and low temperatures alone. Aconitic acid, a component of the TCA cycle, was completely inhibited by the combined treatment. Conclusions: These results suggest that treatment-specific indicators could be useful biomarkers to indicate the synergistic effects of PH3 and low temperature on energy metabolism. [ABSTRACT FROM AUTHOR]

In the Morita‐Baylis‐Hillman (MBH) reaction, a nucleophile undergoes β‐addition to activated alkenes or alkynes, forming reactive intermediates for subsequent carbon‐carbon or carbon‐hetero bond formation. By using a π‐conjugated acceptor, however, an unprecedented reactivity of 1,3‐enynoates and indane‐1,3‐diones was uncovered in the presence of phosphines. When indan‐1,3‐diones were used, γ‐addition of phosphines to 1,3‐enynoates was observed for the first time; moderate to good yields were obtained for 14 substances containing the prominent spirocyclopropane scaffold with 100 % retention of (Z)‐alkene. When 2‐methyl‐indan‐1,3‐diones were used, di(tri)‐substituted furans were produced through the δ‐addition pathway, with 20 substances and a yield of up to 88 % being achieved. Control experiments and density functional theory calculations were conducted to obtain insights into the unconventional γ‐addition reaction pathway. [ABSTRACT FROM AUTHOR]

Trivalent phosphine catalysis is mostly utilized to activate the carbon‐carbon multiple bonds to form carbanion intermediate species and is highly sensitive to certain variables. Random manual multi‐variables are critical for understanding the batch disabled regeneration of trivalent phosphine chemistry. We need the artificial intelligence‐based system which can change the variable based on previously conducted failed experiment. Herein, we report an auto‐optimized electro‐micro‐flow reactor platform for the in‐situ reduction of stable P(V) oxide to sensitive P(III) and further utilized the method for Corey‐Fuchs reaction. [ABSTRACT FROM AUTHOR]

The Wittig reaction is renowned as exceptionally versatile method for converting a diversity of aldehydes and ketones into alkenes. Recently, strategies for chiral phosphine catalysis under PIII/PV=O redox cycling emerged to render this venerable transformation stereoselective. Herein, we describe that phosphine redox catalysis enables the enantioselective synthesis of pertinent biaryl atropisomers by means of a stereocontrolled arene‐forming Wittig reaction. Key to the process is the release of an endogenous base from readily accessible tert‐butyloxycarbonylated Morita–Baylis–Hillman adducts triggered by catalyst intramolecularization, permitting mild phosphine redox catalysis for atroposelective Wittig reactions. By this strategy, a broad diversity of biaryl atropisomers is obtained with up to 94 : 6 enantioselectivity. [ABSTRACT FROM AUTHOR]

Boraadamantanes are a privileged class of caged group 13 compounds having a trigonal pyramidal (non-VSEPR) ground-state. The Lewis acid–base chemistry of this type of compound is underdeveloped when compared to acyclic derivatives. This report provides the first examples of bifunctional boraadamantanes with an appended phosphine moiety (also the first boraadamantanes having a phosphorus–boron bond). Using this scaffold, boraadamantane coordination compounds are accessed for the first time. [ABSTRACT FROM AUTHOR]

The development of efficient and stable non-precious bifunctional electrocatalysts is of great significance, but it remains a great challenge. Herein, we have constructed Co/CoP@NC heterojunction catalyst loaded with Co and CoP particles on a nitrogen-doped carbon (NC) substrate using the pyrolysis-oxidation-phosphating strategy. The synergistic effect of Co and CoP particles on the NC substrate increases the active specific surface area, accelerates the charge transfer rate, and improves the intrinsic activities of the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). The Co/CoP@NC catalyst exhibits superior HER and OER performance. Specifically, the overpotentials required for Co/CoP@NC to reach the current density of 10 mA cm−2 are 142 and 186 mV for HER and OER, respectively. This study provides new insights into the design and synthesis of efficient and stable Co-based heterostructure catalysts. [Display omitted] • Co/CoP@NC is prepared by the pyrolysis-oxidation-phosphating strategy. • Co/CoP@NC has a larger specific surface area and faster charge transfer. • The OER performance of Co/CoP@NC is better than commercial Ir/C at 10 mA cm−2. • Only 1.67 V is needed for Co/CoP@NC to drive 10 mA cm−2 for overall water splitting. [ABSTRACT FROM AUTHOR]

Catalysis has been at the forefront of the developments that has revolutionised synthesis and provided the impetus in the discovery of platform technologies for efficient C−C or C−X bond formation. Current environmental situation however, demands a change in strategy with catalysis being promoted more in solvents that are benign (Water) and for that the development of hydrophilic ligands (especially phosphines) is a necessity which could promote catalytic reactions in water, allow recyclability of the catalytic solutions and make it possible to isolate products using column‐free techniques that involve lesser usage of hazardous organic solvents. In this review, we therefore critically analyse such catalytic processes providing examples that do follow the above‐mentioned parameter. [ABSTRACT FROM AUTHOR]

Three new palladium(II)-iminophosphine complexes, [Pd(L1)(Cl)2] C1, [Pd(L2)(Cl)2] C2 and [Pd(L3)(Cl)2] C3 have been synthesized and successfully characterized by using 1H-NMR, 13C-NMR, 31P-NMR, UV–Vis, FT-IR and magnetic susceptibility techniques. Catalytic activities of complexes towards Suzuki–Miyaura C–C coupling reactions between phenylboronic acid and several aryl halides were investigated under several reaction conditions (solvent, temperature, base, reaction time, and type of substrate). Under optimum conditions, achieving high yields of up to 99% was possible. When 1-bromo-4-nitrobenzene was used for complex C1, bromobenzene for complex C2, and bromobenzene for complex C3, product yields of 99, 99, and 98% were achieved, respectively. Three new palladium complexes bearing iminophosphine ligands was synthesized and successfully characterized. Catalytic activities of the synthesized complexes were investigated on Suzuki–Myaura type coupling reaction between phenylboronic acid and several aryl halides. All complexes exhibited good catalytic activities on C–C coupling reactions up to 99% product formations under mild conditions. [ABSTRACT FROM AUTHOR]

Mixed-ligand complexes of Pd(II) and Pt(II) with 2H-benzo[e][1,3] oxazine-2,4(3H)-dione (HBzoxe), tertiary phosphines (dppe, dppp, dppf and Ph3P), 2,2′-bipyridine (Bipy) and 1,10-phenanthroline (Phen) have been synthesized and characterized by molar conductance measurements, elemental analysis, IR and NMR (1H, 13C and 31P) spectroscopy. In addition, the antimicrobial activity assay studies. The results showed that the HBzoxe ligand behaves as a bidentate chelation ligand through the O and N atoms in [M(Bzoxe)2] {MII = Pd(1) and Pt(2)} complexes, whereas it acts as monodentate ligand through the oxygen atom in complexes (3–14) to afford a square planner geometry around Pd(II) and Pt(II) for all of the complexes. All of the complexes were moderately active on all the bacteria tested (Staphylococcus aureus and Escherichia coli). Hirshfeld surface analysis was carried out to investigate the cooperative non-covalent supramolecular interactions within the various complexes. [ABSTRACT FROM AUTHOR]

The molecular structure of tricarbonyl[η4-6-exo-(triphenylphosphino)cyclohepta-2,4-dien-1-one]iron(0) tetrafluoroborate dichloromethane hemisolvate, [Fe(C28H22O4)(CO)3]BF4·0.5CH2Cl2, as determined by single-crystal X-ray diffraction is reported. The two independent tricarbonyl[η4-6-exo-(triphenylphosphino)cyclohepta-2,4-dien-1-one] iron(0) cations and their corresponding anions form dimers, which constitute the asymmetric unit of the structure parallel to the (100) plane. Solid-state stability within that asymmetric unit as well as between neighboring dimeric units is afforded by C—H...O and C—H...F hydrogen bonds and C—H...π and Y—X...π (Y = B, C; X = F, O) interactions, which yield diperiodic sheets and a three-dimensional extended network.

Xanthene‐backbone FLPs featuring secondary borane functions −B(ArX)H (where ArX=C6F5 (ArF) or C6Cl5 (ArCl)) have been targeted through reactions of the dihydroboranes Me2S ⋅ BArXH2 with [4,5‐xanth(PR2)Li]2 (R=Ph, iPr), and investigated in the synthesis of related cationic systems via hydride abstraction. The reactivity of these systems (both cationic and charge neutral) with ammonia have been probed, with a view to probing the potential for proton shuttling via N−H bond 'activation.' We find that in the case of four‐coordinate boron systems (cationic or change neutral), the N−H linkage remains intact, supported by a NH⋅⋅⋅P hydrogen bond which is worth up to 17 kcal mol−1 thermodynamically, and enabled by planarization of the flexible xanthene scaffold. For cationic three coordinate systems, N‐to‐P proton transfer is viable, driven by the ability of the boron centre to stabilise the [NH2]− conjugate base through N‐to‐B π bonding. This proton transfer can be shown to be reversible in the presence of excess ammonia, depending on the nature of the B‐bound ArX group. It is viable in the case of C6F5 substituents, but is prevented by the more sterically encumbering and secondary donor‐stabilising capabilities of the C6Cl5 substituent. [ABSTRACT FROM AUTHOR]

As an emerging material with the potential to combine the high efficiency of homogeneous catalysts and high stability and recyclability of heterogeneous catalysts, metal‐organic frameworks (MOFs) have been viewed as one of the candidates to produce catalysts of the next generation. Herein, we heterogenized the highly active mono(phosphine)‐Pd complex on surface of UiO‐66 MOF, as a catalyst for Suzuki and Heck cross coupling reactions. The successful immobilization of these Pd‐monophosphine complexes on MOF surface to form UiO‐66‐PPh2–Pd was characterized and confirmed via comprehensive set of analytical methods. UiO‐66‐PPh2–Pd showed high activity and selectivity for both Suzuki and Heck Cross Coupling Reactions. This strategy enabled facile access to mono(phosphine) complexes which are challenging to design and require multistep synthesis in homogeneous systems, paving the way for future MOF catalysts applications by similar systems. [ABSTRACT FROM AUTHOR]

The synthesis of phosphine acetylide amidinate stabilized copper(I) and gold(I) heterobimetallic complexes was achieved by reacting ligand [{Ph2PC≡CC(NDipp)2}Li(thf)3] (Dipp=2,6‐N,N′‐diisopropylphenyl) with CuCl and Au(tht))Cl, yielding the eight membered ring [{Ph2PC≡CC(NDipp)2}2Cu2] and the twelve membered ring [{Ph2PC≡CC(NDipp)2}2Au2]. {Ph2PC≡CC(NDipp)2}2Cu2] features a Cu2 unit, which is bridged by two amidinate ligands, served as a metalloligand to synthesize the heterobimetallic CuI/AuI complexes [{(AuX)Ph2PC≡CC(NDipp)2}2Cu2] (X=Cl, C6F5). In these reactions, the central ring structure is retained. In contrast, when the twelve membered ring [{Ph2PC≡CC(NDipp)2}2Au2] was reacted with CuX (X=Cl, Br, I and Mes), the reaction led to the rearrangement of the central ring structure to give [{(AuX)Ph2PC≡CC(NDipp)2}2Cu2] (X=Cl, Br, I and Mes), which feature the same the eight membered Cu2 ring as above. These compounds were also synthesized by a one‐pot reaction. The luminescent heterobimetallic complexes were further investigated for their photophysical properties. [ABSTRACT FROM AUTHOR]

Gastric cancer prognosis is still notably poor despite efforts made to improve diagnosis and treatment of the disease. Chemotherapy based on platinum agents is generally used, regardless of the fact that drug toxicity leads to limited clinical efficacy. In order to overcome these problems, our group has been working on the synthesis and study of trans platinum (II) complexes. Here, we explore the potential use of two phosphine-based agents with the general formula trans-[Pt(amine)Cl2(PPh3)], called P1 and P2 (with dimethylamine or isopropylamine, respectively). A cytotoxicity analysis showed that P1 and especially P2 decrease cell viability. Specifically, P2 exhibits higher activity than cisplatin in gastric cancer cells while its toxicity in healthy cells is slightly lower. Both complexes generate Reactive Oxygen Species, produce DNA damage and mitochondrial membrane depolarization, and finally lead to induced apoptosis. Thus, an intrinsic apoptotic pathway emerges as the main type of cell death through the activation of BAX/BAK and BIM and the degradation of MCL1. Additionally, we demonstrate here that P2 produces endoplasmic reticulum stress and activates the Unfolded Protein Response, which also relates to the impairment observed in autophagy markers such as p62 and LC3. Although further studies in other biological models are needed, these results report the biomolecular mechanism of action of these Pt(II)-phosphine prototypes, thus highlighting their potential as novel and effective therapies. [ABSTRACT FROM AUTHOR]

Storage insect pest sawtoothed grain beetle, Oryzaephilus surinamensis, is one of the important secondary pests encountered in grains and packaged commodities. It is emerging as one of the important storage pests due to the development of resistance against phosphine fumigants in many countries. Several studies were carried out to ascertain the susceptibility of this pest to phosphine fumigation from India. Dose-response probit assays conducted against larval (second and fourth instar) and adult stages of O. surinamensis revealed significant dose-dependent and time-dependent variations in these stages. The adults were relatively less susceptible to phosphine (LC50 = 36.84 ppm) than the larval stages (LC50 = 13.12, 18.68 ppm respectively, for second and fourth instar at 72 h exposure). Comparative toxicity of phosphine at 24, 48 and 72 h exposures revealed that extended exposures led to linear decrease in lethal concentrations irrespective of life stage of the pest. The discriminating dose bioassay at 0.04-0.2 mg l-1 phosphine with 20 h exposure revealed weak resistance to phosphine in this population. The present study confirmed the tolerance of O. surinamensis to phosphine as comparable with that reported from other countries. Large-scale sampling of field populations of O. surinamensis from different geographical regions will update the current levels of resistance in field populations of O. surinamensis from India. [ABSTRACT FROM AUTHOR]

Surface reconstruction that produces real active species for catalytic reactions generally occurs during electrocatalytic water splitting, but overcoming the reconstruction level‐mass activity‐stability trade‐off is a grand challenge. A cation‐doping in conjunction with a geometrical topology strategy is proposed to concurrently realize deep reconstruction and self‐optimization of FeNi phosphide nanoarrays during an electrochemical activation process. The doped Zn cation induces a deep reconstruction of FeNiP@Fe2P precatalyst by continuously dissolving Fe2P and re‐depositing as amorphous FeOOH that solders Ni2P nanoparticles, forming small ultra‐thin nanosheets with abundant amorphous‐crystalline interfaces for structural stability. Moreover, multichannel topology exhibits an unusual ability to optimize their morphology via finally evolving into multi‐microchannel tubular nanoarrays comprising of interconnected‐nanosheets with a very loose structure for enhanced electrolyte permeability, mass transfer, and accessibility of active sites. The reconstructed Zn‐Ni2P/FeOOH superstructure catalysts reach 10 mA cm−2 current density at an ultra‐low overpotential of 11 mV for hydrogen evolution reactions (HER). Impressively, when assembled as a two‐electrode cell with Zn‐FeNiP@Zn‐Fe2P as anode and Zn‐Ni2P/FeOOH as cathode, it delivers current densities of 10 mA cm−2 at a record low cell voltage of 1.40 V. This strategy provides a novel avenue to promote reconstruction for achieving high catalytic performance. [ABSTRACT FROM AUTHOR]

We synthesized arsenic analogs of a tridentate PPP ligand, bis[2‐(diphenylphosphino) phenyl] phenylphosphine, achieving yields of 40 % to 71 %. Additionally, we prepared copper (I) halide (CuX, X=Br, I) complexes with these ligands, with yields between 43 % and 84 %. Using both experimental and computational methods, we examined their structures and photophysical characteristics. Single crystal X‐ray diffraction showed that all eight complexes had distorted tetrahedral geometries. These complexes exhibited photoluminescence with emission bands peaking from 506 nm to 551 nm and quantum yields up to 0.92 at room temperature. Emission lifetimes varied and showed no direct correlation with quantum yields or wavelengths. Physical manipulation and solvent variations significantly altered their photoluminescent properties. DFT and TD‐DFT calculations revealed that higher arsenic content increased spin‐orbit coupling constants, with iodide complexes performing better than bromide ones due to heavier elements enhancing spin‐orbit coupling. Substituting phosphorus with arsenic significantly affected the luminescence quantum yield and lifetime, demonstrating the heavy‐atom effect of arsenic. The position of arsenic in the ligands critically influenced the photophysical outcomes of the CuX complexes. [ABSTRACT FROM AUTHOR]

Background: Phosphide metal poisoning results in tens of thousands of fatalities per year worldwide. The mortality in critically ill patients often exceeds 50%. The available treatment is supportive and there is no antidote. Dialysis is recommended to treat advanced complications but has not been prescribed early in the process. In this study we report our experience in using dialysis in the early hours of presentation of the patients and suggest it can favorably improve the prognosis. We also draw attention to the risk of suicide under conditions of chronic conflict such as those in northwestern Syria, and to the lack of necessary mental health support for patients after suicide attempts. Methods: Retrospective review of records of patients poisoned with aluminum phosphide and admitted to critical care facilities in northwestern Syria between July 2022 and June 2023. Results: During the observation period 16 cases were encountered. Suicide was the reason of the poisoning in 15 patients, the median patient age was 18 years and over two thirds of the patients were female. Early dialysis was used in 11 patients who were critically ill and their mortality rate was 18%. Conclusions: Phosphide metal poisoning is common in the disasters stricken area of northwestern Syria. Most cases are suicidal and impact young females. Early dialytic interventions may favorably impact the outcomes. [ABSTRACT FROM AUTHOR]

The agricultural fumigant pesticide aluminum phosphide (AlP) is cardiotoxic. Water causes AlP to emit phosphine gas, a cardiac toxin that affects heart function and causes cardiogenic shock. AlP poisoning's high fatality rate is due to cardiotoxicity. This study examines how resveratrol reduces oxidative stress, mitochondrial activity, and apoptosis in human cardiac myocyte (HCM) cells. After determining the optimal doses of resveratrol using the MTT test, HCM cells were subjected to a 24-h treatment of resveratrol following exposure to AlP (2.36 μM). The levels of reactive oxygen species (ROS), superoxide dismutase (SOD) activity, mitochondrial swelling, mitochondrial cytochrome c release, and mitochondrial membrane potential (MMP) in HCM cells were investigated. Also, the expression of Bax and Bcl-2, caspace-3 activity, and apoptosis were assessed. The present investigation revealed that AlP substantially increased the level of ROS and decreased SOD activation, which were significantly modulated by resveratrol in a dose-dependent manner. Moreover, AlP induced an elevation of mitochondrial swelling, cytochrome c release, and MMP collapse. Co-administration of resveratrol significantly reduced above mitochondrial markers. AlP also significantly upregulated BAX and downregulated Bcl-2 expression, elevated caspace-3 activity, and apoptosis. Resveratrol co-administration was able to meaningfully modulate the mentioned parameters and finally reduce apoptosis. In conclusion, resveratrol, via its pleotropic properties, significantly demonstrated cytoprotective effects on HCM cytotoxicity induced by AlP. [ABSTRACT FROM AUTHOR]

A procedure utilizing [TBA][P(SiCl3)2] as P source for the synthesis of phosphinecarboxamides is presented. The synthesis involves the reaction of [TBA][P(SiCl3)2] with isocyanates. These compounds act as highly effective reagents for the subsequent phosphination of isocyanates, leading to the formation of phosphine(triscarboxamides). This reaction proceeds swiftly under mild and straightforward conditions, making it suitable for a wide range of commercially available isocyanates. [ABSTRACT FROM AUTHOR]

Polysubstituted acrylamides are ubiquitous in bioactive molecules and natural products. However, synthetic methods for the assembly of these important motifs remain underdeveloped. Herein, we report the expedient synthesis of structurally diverse and synthetically challenging polysubstituted acrylamides from readily available aromatic amines, cyclopropenones (CpOs), and aryl halides via the synergistic merging of nucleophilic phosphine-mediated amidation and palladium-catalyzed C–H arylation. The reaction is scalable, and some obtained acrylamides proved to be solid state luminogens with obvious aggregation-induced emission (AIE) properties, demonstrating the synthetic potential in drug discovery and material development. [ABSTRACT FROM AUTHOR]

We have found that amines significantly accelerate iodide substitution in CpFe(CO)2I (1) (Cp = η5-cyclopentadienyl) with phosphines and allow the synthesis of new complexes that are not available through reactions carried out without an amine. The reaction of equimolar amounts of 1 and triphenylphosphine in toluene containing DIPA afforded [CpFe(CO)2PPh3]+I− within 5 min at room temperature in 72% yield (90% after 24 h). DIPA and pyrrolidine gave the highest yields of the tested amines. We performed a similar reaction using model bisphosphines 1,3-bis(diphenylphosphino)ethane (dppe) and 1,1′-bis(diphenylphosphino)ferrocene (dppf). The products depended on the reagent ratio and bore the CpFe(CO)2 moiety coordinated to one or two phosphine phosphorus atoms. Chelates [CpFe(CO)(dppe)]+I− (4) and [Cp2Fe2(CO)4(dppe)]2+2I− (5) were formed in 72% and 98% yield, respectively. We also performed the DIPA-catalyzed reaction of 1 with triethyl phosphite and obtained the product of an Michaelis–Arbuzov-like rearrangement, CpFe(CO)2[P(O)(OCH2CH3)2] (11). All complexes were characterized with spectroscopic analysis by NMR, FT-IR, and ESI-MS, and by XRD for three complexes. To clarify the reaction mechanism, we performed theoretical calculations of the intermolecular interactions between 1 and amine molecules. We propose two possible reaction mechanisms to explain the formation of products. [ABSTRACT FROM AUTHOR]

The Mitsunobu reaction is a widely used organic reaction that allows for the replacement of hydroxyl groups with other compounds. It has been extensively studied, with various investigations into its mechanism and intermediates. The reaction has some drawbacks, but many variations and catalytic processes have been developed to address these issues. The studies discussed in the article provide evidence for different intermediates and explore factors that influence the reaction outcome. While there are still unanswered questions, the Mitsunobu reaction is recognized as a valuable and predictable organic reaction. [Extracted from the article]

This study shows the exploration of the gas‐sensing capabilities of C6N8 material against toxic gases like phosphine (PH3) and phosphorous trichloride (PCl3). First‐principles study based on M05‐2X/LanL2DZ (d, p) method was performed to investigate the interaction energy (Eint.), frontier molecular orbitals (FMOs), natural bonding orbital (NBO), noncovalent interactions (NCIs), partial density of states (PDOS), molecular electrostatic potential (MEP), and quantum theory of atoms in molecules (QTAIM) analyses. The interaction energy results showed that PCl3@C6N8 (−23.45 kJ/mol) is more stable than PH3@C6N8 (−14.79 kJ/mol). A considerable decrease in the HOMO‐LUMO band gap of C6N8 was observed as a result of its complexation with the analytes. QTAIM and NCI analyses indicated the presence of weak noncovalent interactions between C6N8 and gases (PH3 and PCl3). SAPT0 analysis was performed to quantify the NCIs. MEP maps of complexes revealed the localization of electronic density on C6N8. The little recovery time of complexes (determined at 300 K) showed that C6N8 can serve as a reusable sensing material against PH3 and PCl3. Our results demonstrate that the C6N8 surface is a reliable material for detecting phosphine and phosphorous trichloride gases. [ABSTRACT FROM AUTHOR]

Herein, we present a CuI-dimer, [CuI{Ph2PC6H4C(O)NC6H4PPh2-o}]2, which catalyzed direct C(sp3)–H homocoupling of benzyl and cycloalkane derivatives with excellent yields and regio-selectivity. The method is very simple and tolerates various functionalities. Synergistic metal–ligand cooperativity was observed in Cu–N bond cleavage and protonation of nitrogen, and facilitates a bifunctional pathway, minimising the free energy corrugation for catalytic intermediates. [ABSTRACT FROM AUTHOR]

Neutral Cu(I) complexes containing Schiff bases as chelating N‐donors and phosphines as P‐donors were efficiently isolated and characterized. The imines were obtained by straightforward condensation between pyrrole‐2‐carboxaldehyde and the corresponding aromatic amines. The structure of most of the Cu(I) species was elucidated through single‐crystal X‐ray diffraction. The Cu(I) complexes exhibited intense absorptions around 400–500 nm ascribed to MLCT transitions. For some Cu(I) derivatives, orange‐ and red‐orange emissions were detected upon excitation with near‐UV and blue irradiation in the solid state. The emission maxima were red‐shifted once the benzothiazole‐derived Schiff base or Xantphos were employed as chelating ligands. Microsecond‐long lifetimes, wide emissions, and large Stokes shifts suggest the involvement of triplet states in the luminescent process. Electrochemical measurements and DFT calculations were employed to rationalize the photoluminescence properties, which were ascribed to mixed 3LC/3MLCT transitions. [ABSTRACT FROM AUTHOR]

The reactivity of complexes [Fe2(μ‐S2)(CO)4L2] (L=CO (1), PPh3 (2)), with lithium alkynylide reagents generated in situ, was investigated. The behavior of the S2‐bridge in these compounds depends on the substitution at the diiron core. The reaction with the hexacarbonyl derivative 1 leads to the formation of the 1,2‐dithiolene bridged complex [Fe2(μ‐SCH=C(R)S)(CO)6] (3R) while the molecule [Fe2(μ‐SH)(μ‐SC≡CR)(CO)4(PPh3)2] (5R), with an open butterfly structure, is isolated when reacting the disubstituted derivative 2. The disubstituted dithiolene complex [Fe2(μ‐SCH=C(Ph)S)(CO)4(PPh3)2] (4Ph) can only be obtained by substitution of carbonyls with PPh3 in 3R. In the presence of piperidine, 5R isomerizes into the 1,1'‐dithiolene bridged derivative 6Ph. The novel compounds 4–6 were synthesized and characterized by IR and NMR spectroscopies. X‐ray crystallographic studies of the dithiolene complexes 3Ph–4Ph allowed their structural analysis. [ABSTRACT FROM AUTHOR]

A series of new pyrazole‐alkyl phosphine ligands with varying cycloalkyl ring sizes that enable additive‐free regio‐ and chemoselective C─H arylation of heterocycles are reported. Excellent α/β selectivity of various heterocycles such as benzo[b]thiophene, thiophene, furan, benzofuran, and thiazole can be achieved using these ligands, along with excellent chemoselectivity of C─Cl over C─OTf of chloroaryl triflates. Mechanistic studies supported by both experimental findings and density functional theory calculations indicate that the pyrazole phosphine ligands with optimal ring sizes allow the reaction to proceed with a lower energy barrier via a concerted metalation–deprotonation pathway. [ABSTRACT FROM AUTHOR]

α-Chiral alkyl phosphines are privileged structural motifs with a wide application in organic and medical synthesis. It is highly desirable to develop stereoselective methods to prepare these enantioenriched molecules. The incorporation of C(sp³)-H functionalization and chiral phosphine chemistry is much less explored, probably because of the weak reactivity of C(sp³)-H bonds and/or the challenging site-and stereoselectivity issues. Herein, we disclose a synergistic catalysis system to enable an enantioselective radical addition process of α-substituted vinylphosphine oxides. An array of diverse α-chiral alkyl phosphors compounds is smoothly accessed by using the readily available chemicals as the inert C(sp³)-H bond reagent, such as sulfides, amines, alkenes, and toluene derivatives, exerting remarkable chemo-, site-, and enantioselectivity. On the basis of the mechanistic studies, both the C(sp³)-H bond activation and the stereochemistry-determining step are proposed to involve a single-electron transfer/proton transfer process. [ABSTRACT FROM AUTHOR]

By a reaction of trimethylphosphine with an open‐[60]fullerene, corresponding dimers could be generated via two‐fold deoxygenation processes even though the formation of β‐oxo‐phosphorous ylide is inevitable, a part of which is hydrolyzed to yield an α‐methylene carbonyl derivative. Nevertheless, Wittig reaction and aldol condensation did not proceed well, indicating the presence of an unknown dimerization pathway. In the ylide formation, 1‐phosphonium‐3‐carbabetaine was previously proposed as a key intermediate. Upon assuming that the betaine also participates in the dimerization process, we examined a possible reaction pathway computationally. As the results, the betaine formed by a reaction with the first phosphine was suggested to undergo nucleophilic addition to an unreacted molecule of the open‐[60]fullerene, yielding an epoxide dimer which is then deoxygenated by the second phosphine to furnish the desired open‐[60]fullerene dimer. [ABSTRACT FROM AUTHOR]

This document provides experimental results for the synthesis of various compounds using a general procedure. The compounds include 5-Pivalamidooctyl Benzoate, N-(1-(2-Methoxyphenoxy)heptan-4-yl)pivalamide, N-(1-(3-(Trifluoromethyl)phenyl)heptan-4-yl)pivalamide, 4-Pivalamidoheptyl 2-Bromobenzoate, N-(8-(2,6-Dichlorophenoxy)octan-4-yl)pivalamide, 6-Pivalamidononyl 2-(2-Fluoro-[1,1′-biphenyl]-4-yl)propanoate, 7-Pivalamidodecyl Thiophene-2-carboxylate, and 4-Pivalamidoheptyl 1-Methyl-1H-pyrrole-2-carboxylate. The compounds' yields, physical properties, and spectroscopic data, including NMR and HRMS, are reported. The document does not provide any additional information or context beyond the experimental results. [Extracted from the article]

Homogenous catalysis is an essential tool within the commercial manufacture of bulk and fine chemicals. Within this, phosphine ligands, such as tricyclohexylphosphine, otherwise known as CYTOP® 366, are a crucial component. When designing a pathway to your ligand of choice, some key considerations include safety, yield and quality, but at commercial volumes we must also balance cost and consider the technologies readily available. Herein, we report the synthetic route that was chosen to manufacture tricyclohexylphosphine at commercial scale. We also consider, with the use of computational calculations, why traditional hydrophosphination methods failed, where the selected pathway succeeded. [ABSTRACT FROM AUTHOR]

Phosphine (PH3) is a methyl bromide alternative with the potential to control surface pests of New Zealand avocados as a pre-export disinfestation treatment. 'Hass' avocado fruit were treated with PH3 (as ECO2FUME® (2% PH3, 98% CO2 (w/w); Cytec Industries Inc.)). at 500, 750 and 1,500 ppm for 24, 48 and 72 h at 5–6 °C, along with vials containing mould mites (Tyrophagus communis) and greenhouse thrips (Heliothrips haemorrhoidalis). Fruit were then stored at 5 °C for three weeks, external quality assessed, and internal fruit quality assessed after ripening at 20 °C. PH3 treatments had no impact on external fruit quality, nor on skin colouration, and only minor increase in softening compared to control at 24 h, but not 48 or 72 h. Complete (100%) mortality was achieved for thrips at all PH3 concentrations for 48 h. However, only ∼50% mould mite mortality was achieved at the highest PH3 concentration of 1,500 ppm for 72 h; although this treatment did provide a significant reduction in rots and internal disorders. This initial study demonstrates that longer-duration treatments and higher PH3 concentrations improves fruit quality compared with controls, mainly by reducing rots. These treatments fully controlled thrips but provided only partial control of mould mites. [ABSTRACT FROM AUTHOR]

The one-pot template reaction between 2-(diphenylphosphino)benzaldehyde, benzylamine and copper(I) iodide yields the dinuclear copper complex (P∩N)2Cu2I2, as revealed by single-crystal X-ray diffraction. [ABSTRACT FROM AUTHOR]