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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]

Efficient organic blue materials are essential to develop highly efficient organic light-emitting diodes. However, there is a challenge to commercialize efficient blue compounds due to the fundamentally wide band gap and the lack of pure blue emitters. In this study, the new anthracene-based fluorescent emitter, (4-(10-(4-(9H-carbazol-9-yl)-2-methylphenyl)anthracen-9-yl)-3-methylphenyl)diphenylphosphine oxide (CZm-AN-mPO) was designed and synthesized. The thermal, photophysical and electrochemical properties of the CZm-AN-mPO were systematically investigated. The CZm-AN-mPO exhibits a deep-blue emission at 425 nm and AIE property with a relatively narrow full-width at half maximum of 34 nm. The CZm-AN-mPO based non-doped devices show pure blue emission. The optimized OLEDs indicated maximum external efficiencies of 4.3% and 4.2% at emission layer thickness of 20 nm and 40 nm, respectively. [ABSTRACT FROM AUTHOR]

Triphenylphosphine (TPP) salt derivatives, with their rich chemistry of core-substitution, have emerged as promising candidates for ultralong room temperature phosphorescence (RTP) materials owing to their distinct molecular structures, high quantum efficiency and exceptional phosphorescence properties. This feature article highlights the vast potential of TPP salt derivatives in tunable RTP properties by exploring some factors such as the alkyl chains, halogen anions, through-space charge transfer states, etc., and recent advancements in multi-level information encryption, high-level anticounterfeiting tags and X-ray imaging applications. We anticipate that this article will assist in directing future analyses based on the mechanisms underlying the RTP behavior of TPP derivatives and offer guidance for the rational design of high-performance RTP materials. [ABSTRACT FROM AUTHOR]

The reductive amination of 1,6‐hexanediol with ammonia is one of the most promising green routes for synthesis of 1,6‐hexanediamine. Herein, we developed a phosphorous modified Ni catalyst of Ni−P/Al2O3. It presented satisfactory improved selectivity to 1,6‐hexanediamine in the reductive amination of 1,6‐hexanediol compared to the Ni/Al2O3 catalyst. The phosphorous tended to interact with Al2O3 to form AlPOx species, induced Ni nanoparticle to be flatter, and the decrease of strong acid sites, the new‐formed Ni−AlPOx−Al2O3 interface and the flatter Ni nanoparticle were the key to switch the dominating product from hexamethyleneimine to 1,6‐hexanediamine. This work develops an efficient catalyst for production of 1,6‐hexanediamine from the reductive amination of 1,6‐hexanediol, and provides a point of view about designing selective non‐noble metal catalysts for producing primary diamines via reductive amination of diols. [ABSTRACT FROM AUTHOR]

Rhodium complexes in the −I and 0 oxidation states are of great potential interest in catalytic applications. In contrast to their rhodium +I congeners, however, the structural and electronic parameters governing their access and stability are far less understood. Herein, we investigate the two‐electron reduction of a parameterized series of bis(diphosphine) Rh complexes [Rh(dxpy)2]NTf2 (x=P‐substituent, y=alkanediyl bridging P atoms). Through (electro)reductions from the RhI parents, Rh−Id10‐complexes were obtained and characterized spectroscopically, including 103Rh NMR data. The reductive steps convolute with structural rearrangements from square planar to tetrahedral coordination. We found that the extent of these reorganisations defines whether the first E0(RhI/0) and second E0(Rh0/−I) reduction potentials are normally ordered, leading to monoelectronic stepwise transitions, or inverted, giving bielectronic events. Reductionist approaches based on Hammett parameters or the P−Rh‐P bite angles provide only partial correlations with the redox potentials. However, we identified the C−O stretch of analogue diphosphine complexes as an expedient computational parameter that enables these correlations through both electronic and geometric features, even in a predictive manner. Gaining control over two‐electron reduction behaviors through rationalized ligand effects has potential impact beyond Rh complexes, for molecular and enzymatic metal sites commonly exhibiting bielectronic transitions. [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]

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]

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]

Unsymmetric boron (III) subphthalocyanines with a triselenole ring or a diselenete ring and eight fluoro groups were prepared by the reaction of 5,6‐dicyano‐4,7‐diethylbenzo‐[1,2,3]triselenole and tetrafluorophthalonitrile with trichloroborane in xylene. The reaction was accompanied by a contraction of the triselenole ring to the diselenete ring. The substrate, dicyanobenzo[1,2,3]triselenole, was prepared by a new procedure via a photolytic demethylenation reaction of 3,7‐diethyl[1,3]diselenolophthalonitrile using a 10 W white LED light. While triselenolosubphthalocyanine was treated by triphenylphosphine to give the diselenete derivative, the reaction of diselenetosubphthalocyanine with Woolion's reagent produced the expanded triselenole ring. The diselenete derivative reacted with tetrakis(triphenylphosphine)platinum to yield the corresponding platinum complex with Se−Pt bonds. Q‐band absorption for the products appeared at around λmax=590 nm in the UV‐vis spectrum and weak emission was observed at about λe=620 nm. When diselenetosubphthalocyanine was treated with pentachloro antimonate in dichloromethane or sodium metal in hexane/tetrahydrofuran, the solution showed strong ESR signals. The structures of model compounds were optimized using the DFT method with the Gaussian 09 program at the B3LYP/6‐31G (d, p) level. [ABSTRACT FROM AUTHOR]

The first examples of RE/Si FLPs (RE: rare-earth metal, FLPs: frustrated Lewis pairs), namely Yb/Si FLPs were synthesized, where Yb⋯Si distances are in the range of 3.55 to 3.72 Å. These FLPs react with triphenylphosphine sulfide and aryl isocyanide to produce novel silylyne group transfer products through dissociation of naphthalene. [ABSTRACT FROM AUTHOR]

P‐chiral supramolecular phosphine ligands are crucial for asymmetric transformations, but their synthesis is tedious. We report a one‐step synthesis of thermally stable P‐chiral supramolecular phosphines and their performance in the asymmetric hydrogenation of functionalized alkenes. A rational designing and synthesis of (R, R)‐QuinoxP* ligated palladium complex (Pd‐2) in excellent yield is reported. This Pd‐2 catalyzed a direct P−C coupling of 2,3‐dihydro‐1‐H‐phosphindole (A1)/1,2,3,4‐tetrahydrophosphindoline (A2) with 1‐(3‐iodophenyl)urea (B1)/2‐iodo /6‐hydroxy pyridine (B2) and,produced corresponding ligands L1–L3. The P−C coupling between A1 and B2 produced 6‐(2,3‐dihydro‐1H‐phosphindol‐1‐yl)pyridine‐2(1H)‐one (L2) with an excellent enantiomeric excess of up to 99 %. L2 was found to be remarkably stable even at 150 °C and did not oxidize/hydrolyze for at least 24 hours in open air. Such thermal stability and an impediment to oxidation are unprecedented. L2 self‐assembled and produced L2−C1 (Pt), L2−C2(Pd), and L2−C3(Rh) assemblies. The utility of the self‐assembled P‐chiral ligand was demonstrated in the Rh‐catalyzed asymmetric hydrogenation (AH) of functionalized olefins. The L2−C3 catalyzed AH of functionalized alkenes and delivered chiral products with excellent enantioselectivity of >99 %. A small library of 16 substrates was subjected to AH using L2−C3 to produce chiral compounds with excellent conversion and ee. [ABSTRACT FROM AUTHOR]

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]

Convenient synthesis of phosphorus-containing derivatives of succinic acid, which contain functionalized phosphonous, phosphonic, and phosphinic acid moieties have been developed. The nucleophilic addition of bis(trimethylsiloxy)phosphine to diesters of maleic, itaconic, and acetylenedicarboxylic acids proceeds regioselectively to give a number of functionalized phosphonites. Further aminomethylation of these compounds affords various target acid derivatives. The resulting compounds are of interest as promising biologically active substances and water-soluble ligands. [ABSTRACT FROM AUTHOR]

The poly(vinylpyridine) (PVP) based (co)polymers are of particular interest in materials science, due to their multifunctionality and diverse applications. So far, there is no report on the sequence-regulated copolymerization of vinylpyridines (VPs) and methacrylate monomer in one-step manner yet. Here we designed and synthesized a series of guanidine phosphines as Lewis base (LB), which is combined with bulky organoaluminium to construct Lewis pairs (LPs) for polymerization of VPs. The living/controlled polymerization of 4-vinylpyridine (4-VP) or 2-vinylpyridine (2-VP) can be accomplished with remarkable efficiency by such Lewis pair polymerization (LPP), furnishing polymers with high molecular weight (up to 288 kg/mol) and narrow molecular weight distribution (as low as 1.17). Mechanistic studies reveal the interaction of LPs and formation of zwitterionic intermediates, providing solid evidences to support the proposed polymerization mechanism. More importantly, by simply adjusting the LA dosage, this LPP strategy realizes the unprecedented control over the sequence regulation of 2-VP-based copolymers from gradient to block in one-step manner, regardless of the monomer ratio, which greatly expands the versatility of the LPP. [ABSTRACT FROM AUTHOR]

We report a mild, operationally simple, convenient, and rapid method of peptide bond formation using triphenylphosphine and iodine. The developed protocol was utilized to couple coded, non‐coded, and challenging amino acids in 64–92 % yield. Sterically hindered α,α‐disubstituted amino acids, which are important constituents of natural peptides, were also coupled in good yield. Mild reaction conditions in open air produce peptide bonds in a short time (30 min) without racemization. [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]

A series of new aromatic substituted indanone and indanol building blocks have been prepared and are anticipated to aid future drug discovery studies. In total, seven compounds (7, 12–17) are expounded on, and all have been fully characterized. In doing so, we have shown multiple examples of highly chemoselective reactions. One example employed an adaptation of Fujioka’s chemoselective reduction methodology, allowing an ester to be reduced in the presence of a ketone. In another example, an uncommon benzylic methyl group to aldehyde oxidation was demonstrated for two different compounds. These and other chemoselective interconversions allowed us to identify compound (12) as a remarkably flexible springboard for accessing a diverse array of indan-based building blocks (13–17).

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.

Phosphine is a major fumigant for insects control in stored products. However, the current fumigation with aluminum phosphide to generate phosphine is facing many challenges, such as require manual operation, fumigation produce can’t be automatically performed, and management of residue contaminants. To address these issues, the study utilizes a combination of pure phosphine gas from cylinders and nitrogen from a membrane separation nitrogen generator. Phosphine and nitrogen are mixed at predetermined ratios, and the resulting gas mixture is delivered directly into sealed grain storage facilities via a controlled release device and circulated within the grain piles to ensure fumigant evenly distribution. This maintains effective phosphine concentrations within the storage facility. The exposure duration lasted for 13 days, during which phosphine concentrations were monitored, and the total mortality rate of adult insects within the grain piles was recorded. Within 9 hours of treatment initiation, gas concentrations reached 736 mL/m3, peaking at 1 160 mL/m3, with an effective average concentration above 200 mL/m3 sustained for 10 days. The gas circulated and distributed uniformly within the treated space, enabling effective control of major stored commodity pests within a relatively short exposure period.

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]

Gallylene supported by a bis(oxazolinyl)(phenyl)methanide (Boxm) ligand was synthesized and structurally characterized. The reaction of this gallylene with triphenylphosphine sulfide/selenide yielded dimeric gallium sulfide and selenide. These compounds could be converted to monomeric terminal sulfide and selenide by coordination of an external Lewis base such as an N‐heterocyclic carbene (NHC or IMe4) and 4‐dimethylaminopyridiene (DMAP). These doubly‐base‐stabilized gallium sulfide/selenide reacted with phenyl isocyanate to give the corresponding cycloadducts by releasing the Lewis base, indicating the formation of a single‐base‐stabilized gallium sulfide/selenide intermediate. [ABSTRACT FROM AUTHOR]

Using single‐crystal to single‐crystal solid/gas reactivity the gold(I) acetylene complex [Au(L1)(η2‐HC≡CH)][BArF4] is cleanly synthesized by addition of acetylene gas to single crystals of [Au(L1)(CO)][BArF4] [L1=tris‐2‐(4,4′‐di‐tert‐butylbiphenyl)phosphine, ArF=3,5‐(CF3)2C6H3]. This simplest gold‐alkyne complex has been characterized by single crystal X‐ray diffraction, solution and solid‐state NMR spectroscopy and periodic DFT. Bonding of HC≡CH with [Au(L1)]+ comprises both σ‐donation and π‐backdonation with additional dispersion interactions within the cavity‐shaped phosphine. [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]

The design of iron clusters featuring a bimetallic core and several protonation sites in the second coordination sphere of the metal centers is important for modeling the activity of polymetallic active sites such as the H-cluster of [FeFe]-hydrogenases. For this purpose, the syntheses of complexes [Fe3(CO)5(κ2-PPh2NR2)(μ-pdt)2] (R = Ph (1), Bn (2)) and [Fe3(CO)5(κ2-PPh2NR2)(μ-adtBn)(μ-pdt)] (R = Ph (3), Bn (4)) were carried out by reacting hexacarbonyl precursors [Fe2(CO)6(µ-xdt)] (xdt = pdt (propanedithiolate), adtBn (azadithiolate) with mononuclear complexes [Fe(κ2-pdt)(CO)2(κ2-PPh2NR2)] (PPh2NR2 = (PPhCH2NRCH2)2, R = Ph, Bn) in order to introduce amine functions, through well-known PPh2NR2 diphosphine, into the vicinity of the triiron core. The investigation of the reactivity of these triiron species towards the proton (in the presence of CF3SO3H) and the influence of the pendant amines on the redox properties of these complexes were explored using spectroscopic and electrochemical methods. The protonation sites in such triiron clusters and their relationships were identified. The orientation of the first and second protonation processes depends on the arrangement of the second coordination sphere. The similarities and differences, due to the extended metal nuclearity, with their dinuclear counterparts [Fe2(CO)4(κ2-PPh2NR2)(μ-pdt)], were highlighted. [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]

A new narrowband thermally activated delayed fluorescence emitter, PhCzBN-PO, was developed by incorporating the diphenylphosphine oxide (DPPO) group into a multi-resonance core. The unique properties of DPPO enabled PhCzBN-PO to achieve pure green emission and a nonplanar structure. The resulting electroluminescent devices achieved high external quantum efficiencies up to 32.4% with extremely low efficiency roll-off and pure-green emission with Commission Internationale de L'Eclairage (CIE) coordinates of (0.24, 0.67). [ABSTRACT FROM AUTHOR]

Introduction: Over the last ten years the use of teeth whitening products containing hydrogen peroxide (H2O2) has become popular. According to European legislation, it is allowed to be added to products for both professional and personal use, in concentrations from 0.1 to 6%. Ingestion of low concentrations of hydrogen peroxide in the oral cavity does not lead to adverse effects, but its long-term use can lead to health risks. Aim: Development of a method for the determination of hydrogen peroxide in teeth whitening products. Material and methods: The method is based on the oxidation of hydrogen peroxide with triphenylphosphine (TPP) to triphenylphosphine oxide (TPPO) and the subsequent reverse phase HPLC-UV analysis of TPPO at a wavelength of 255 nm. Results: The method was applied to the analysis of commercial products for personal use containing urea peroxide or sodium percarbonate. Discussion: The results of the analyzed products show compliance of the hydrogen peroxide content with the values in Regulation (EC) No. 1223/2009 of the European Parliament and of the Council of 30 November 2009 on cosmetic products (recast), especially for oral care products - teeth whitening (from 0.1 to 6%). Conclusion: The method is suitable for official control purposes in the working range 30.00 ÷ 180.00 µg of H2O2 per kg product (from 0.08 % to 10% hydrogen peroxide). [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]

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]

This work synthesized new biologically active Cu(I) complexes 1-5, obtained from the reaction of Cu(I) nitrate with different bidentate pyridinyl Schiff base ligands (E)1-(pyridin-2-yl)-N-(p-tolyl)methanimine L1, (E)-1-(pyridin-2-yl)-N-(otolyl) methanimine L2, (E)-N-isopropyl-1-(pyridine-2-yl)methanimine L3, (E)-Nmesityl-(pyridinyl)methanimine L4 and (E)-N-(2,6-dimethylphenyl)-1-(pyridine-2-yl)methanimine L5, with PPh3 ancillary ligand. The metal complexes with general formula [Cu L(PPh3)2]NO3, were characterised by FT-IR, UV-Vis, NMR and MS, X-ray crystallography and elemental analysis. The antibacterial activities against Staphylococcus aureus (SA), Escherichia coli (EC), Klebsiella pneumonia and Pseudomonas aeruginosa (PA) were investigated using agar well diffusion method with ofloxacin as reference. UV-Visible spectra and FT-IR result showed bathochromic shift in the imino (C=N) frequencies in the complexes confirming coordination to the metal centre. Single crystals obtained in complexes 2, 3, 5 revealed orthorhombic crystal systems having Tau (t4) values in the range 0.73 - 0.87 depicting distorted tetrahedral geometries. Coordination to the metal center was bidentate for all the ligands via the pyridinyl N and imine N in conjunction with two triphenylphosphine P in the N^N^P^P fashion in complexes 2, 3, and N^N^P^O fashion in complex 5. The antibacterial activities revealed that all the complexes exhibited better antibacterial activities relative to their parent ligands and PPh3. The study found out that the newly synthesized complexes have better antibacterial performances hence make the metal complexes potential chemotherapeutic agents in drug design. [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]

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]

Three new ruthenium(II) polypyridyl complexes containing α‐diimine ligands, namely, carbonylhydrido(1,10‐phenanthroline‐κ2N,N)bis(triphenylphosphine‐κP)ruthenium(II) hexafluorophosphate, [RuH(C12H8N2)(C18H15P)2(CO)]PF6, carbonylhydrido(2,9‐dimethyl‐1,10‐phenanthroline‐κ2N,N)bis(triphenylphosphine‐κP)ruthenium(II) hexafluorophosphate, and carbonylhydrido(4,7‐dimethyl‐1,10‐phenanthroline‐κ2N,N)bis(triphenylphosphine‐κP)ruthenium(II) hexafluorophosphate, both [RuH(C14H12N2)(C18H15P)2(CO)]PF6, were synthesized and characterized by spectroscopic and X‐ray diffraction methods. In these complexes, the ruthenium(II) ion adopts a distorted octahedral geometry. There are no intermolecular hydrogen bonds in the crystal structures of the analysed complexes and Hirshfeld surface analysis showed that the H...H contacts constitute a high percentage, close to 50%, of the intermolecular interactions. [ABSTRACT FROM AUTHOR]

A convenient synthesis of functionalized aminoalkyl organophosphorus compounds bearing 3-, 4- or 5-coordinated phosphorus atom is based on readily available enamines and trivalent phosphorus acid esters. Radical addition of bis(trimethylsiloxy)phosphine to enamines proceeds regioselectively to give aminoalkylphosphonites, and their subsequent functionalization affords various derivatives of the target acids. The nucleophilic addition of hydrospirophosphorane to enamines also proceeds regioselectively to furnish α-aminoalkyl spirophosphoranes containing five-coordinated phosphorus atom. The resulting compounds are of interest as promising biologically active substances and water-soluble ligands. [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]

Circular dichroism (CD) studies on poly(1,4‐phenylene)s bearing a chiral side chain in the aggregated conditions were carried out. Little CD was observed in a solution form, while addition of a poor solvent into the polyphenylene solution induced aggregation and a strong CD was observed, accordingly. Applying the controlled degree of polymerization (DP) of poly(1,4‐phenylene) in the use of bidentate diphosphine Chiraphos as a ligand for the nickel catalyst, the relationship of DP with CD strength was studied to reveal to show the highest CD at the DP=84 (gabs=ca. 2×10−2). It was also found that the related aggregation was observed in good solvent 1,2‐dichloroethane upon standing the solution at 4 °C for 3–23 days to observe gabs=ca. 10−1. Studies on the substituent effect of poly(1,4‐phenylene) suggested that CD behaviors were dependent on the type of non‐chiral substituent on the aromatic ring as well as the side‐chain chirality. [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]

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]

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]

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]

Np(IV) Lewis base adducts were prepared by ligand substitution of NpCl4(DME)2. Using acetonitrile and pyridine, NpCl4(MeCN)4 (1) and NpCl4(pyr)4 (2) were isolated, respectively. Addition of t-butylbipyridine and triphenylphosphine oxide generated the respective Lewis base adducts, NpCl4( tBuBipy)2 (3) and NpCl4(OPPh3)2 (4). All species were fully characterized using spectroscopic and structural analyses. [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]

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]

The reaction of a square-planar platinum(II) complex containing two bis(2-diphenylphosphinoethyl)phenylphosphine (triphos), [Pt(triphos)2](NO3)2, with [Au(tu)2]Cl (tu = thiourea) gave a new trinuclear AuI2PtII complex, [Pt(triphos)2{Au(tu)}2]Cl2(NO3)2, through Au-P coordination. While the [Pt(triphos)2]2+ unit in [Pt(triphos)2](NO3)2 adopted the trans-meso configuration, only the cis-racemic isomer was observed for [Pt(triphos)2{Au(tu)}2]Cl2(NO3)2. 31P NMR spectroscopy indicated rapid equilibrium among the possible isomers of [Pt(triphos)2]2+, which facilitated the trans-to-cis transformation at the PtII center in this system. Additionally, we observed that this structural transformation led to an increase in the emission intensity. [ABSTRACT FROM AUTHOR]