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In this study, we investigated the impact of adding Triphenylphosphine (TPP) at concentrations of 1 wt.%, 3 wt.%, and 5 wt.% to an epoxy-anhydride system that displays, a degradation in mechanical properties at high temperatures. We conducted an analysis of cure behavior using differential scanning calorimetry and evaluated flexural, shear, and tensile strengths at room temperature. To assess heat resistance, CFRP specimens were exposed to 100∘C for 1 h, and tensile strengths were subsequently measured. The addition of 3 wt.% TPP resulted in a 5 min reduction in the time required to reach a 95% degree of cure, but it was observed that mechanical properties at room temperature were compromised. CFRP exposed to 100∘C indicated that an increase in TPP content helped mitigate the degradation of mechanical properties. [ABSTRACT FROM AUTHOR]

A series of heteroleptic copper(I) β-diketiminate triarylphosphine complexes is reported, having the general formula Cu(R¹NacNacR2)(PPhX3), where R¹NacNacR2 is a substituted β-diketiminate and PPhX3 is a triphenylphosphine derivative. A total of five different R¹NacNacR2 ligands and three different triarylphosphines are used to assemble the nine complexes. The syntheses, X-ray crystal structures, cyclic voltammograms, and UV–vis absorption spectra of all compounds are described. Whereas most of the compounds are weakly luminescent or only luminesce at 77 K, the four complexes with the more sterically encumbered β-diketiminate ligands, with methyl or isopropyl substituents at the 2- and 6-positions of the N-phenyl rings, exhibit weak room-temperature photoluminescence with peaks between 519 and 566 nm and long excited-state lifetimes in the range of 15–70 μs. The sterically encumbering substituents in this subset have subtle effects on the UV–vis absorption maximum, which red shifts slightly as the steric bulk increases, as well as significant effects on the photoluminescence lifetime, which is observed to increase as the steric bulk is augmented. Substituents on the triarylphosphine also influence the excited-state dynamics in the bulky complexes, with the more electron-rich tris(4-methoxyphenyl)phosphine (PPhOMe3) giving longer-excited-state lifetimes compared to triphenylphosphine (PPh3) when the same R¹NacNacR2 ligand is used. [ABSTRACT FROM AUTHOR]

A base-promoted olefination reaction between alkylphosphonium salts and activated alkyl halides has been developed. The products were obtained in excellent E -selectivity. In contrast to most other olefination reactions of phosphonium salts, the reaction yields triphenylphosphine as the main by-product, which can be directly reused in the formation of new phosphonium salts. [ABSTRACT FROM AUTHOR]

A switchable, solvent-free catalytic system was developed in which Al methyl aminebis(phenolate) catalysts selectively initiate the formation of a polyether from cyclohexene oxide under CO2 atmosphere or the ring opening copolymerisation (ROCoP) of cyclohexene oxide and CO2 through the addition of a PPNCl (bis(triphenylphosphine)iminium chloride) cocatalyst to form poly(cyclohexene carbonate). [ABSTRACT FROM AUTHOR]

The heterometallic [Ag(I)/Fe(II)] molecular electrocatalysts for hydrogen production were introduced here to recognize the mutual role of metallic nuclearity and ligand engineering. A series of ferrocenyl dithiophosphonate stabilized mononuclear [Ag(PPh3)2{S2PFc(OR)}] {where R=Me (1), Et (2), nPr (3), iPr (4), iAmyl (5); Fc=Fe (ɳ5‐C5H4) (ɳ5‐C5H5)} and dinuclear [Ag(PPh3){S2PFc(OR}]2 {where R=Et (2 a), and nPr (3 a)} complexes were synthesized and characterized by SCXRD, NMR (31P and 1H), ESI‐MS, UV‐Vis, and FT‐IR spectroscopy. The comparative electrocatalytic HER behavior of 1–5 and 2 a–3 a showed effective current density of 1 mA/cm2 with overpotentials ranging from 772 to 991 mV, demonstrating the influence of extended and branched carbon chains in dithiophosphonates and metallic (mono‐/di−) nuclearity, which correlates with documented tetra‐nuclear [Ag4(S2PFc(OnPr)4], 6. DFT study suggests the coordinated (μ1‐S) site of ligands is the reactivity center and the adsorption energy of intermediate [H*‐SM] varies with the engineering of ligand and nuclearity. A catalytic mechanism using mononuclear (1) and di‐nuclear (2 a) was proposed with the assistance of DFT. Each complex, being the first example of Ag(I) dithiophosphonates, exhibits intense photoluminescence with high quantum yields ranging from 33 % to 67 %. These results link the lower nuclearity structures to their physical and catalytic properties. [ABSTRACT FROM AUTHOR]

A method was developed for the synthesis of new unsymmetrical cage phosphonates containing terminal halo(bromo, chloro)methyl groups as a result of the reaction of (2-ethoxyvinyl)phosphonic dichloride with halogen-N-(3-hydroxyphenyl)acetamides in trifluoroacetic acid. New cage phosphonates containing one or two phosphonium groups were obtained as a result of the reaction of triphenylphosphine with the corresponding cage phosphonates. It was shown that the type of products formed in this reaction depends on the nature of the halogen atom in the halomethyl group of the cage phosphonate. [ABSTRACT FROM AUTHOR]

Perovskite nanograins with a dimension larger than the Bohr exciton diameter have significant advantages in achieving high‐performance light‐emitting diodes (LEDs) due to their bandgap uniformity and strong charge confinement effect. However, perovskite nanograin films prepared by the solution spin‐coating method are prone to produce massive defects due to the fast crystallization rate, leading to severe nonradiative recombination that greatly detracts the performance of LEDs. Therefore, regulating crystallization and minimizing defects plays a crucial role in the development of perovskite nanograins for high‐performance LEDs. Herein, a simple dual‐additive strategy is reported to manipulate the growth of high‐quality CsPbBr3‐based nanograin films. A multifunctional additive 5‐aminovaleric acid (5AVA) is introduced to slow down the crystallization rate of CsPbBr3, followed by the further addition of triphenylphosphine oxide (TPPO) to achieve effective synergistic passivation of defects, which can significantly enhance radiative recombination rate and reduce defects‐induced nonradiative recombination. Ultimately, based on the 5AVA and TPPO co‐modified CsPbBr3 nanograins, the perovskite LEDs are fabricated achieving a maximum external quantum efficiency (EQE) of 20.95% and an average EQE of approaching 20%, demonstrating excellent reproducibility. This work provides new insight into the crystallization regulation and defect passivation of perovskite nanograins and the further improvement of device performance. [ABSTRACT FROM AUTHOR]

Grasping the behavior of metal nanoclusters in solution at the atomic level is a pinnacle challenge in nanoscience. In addressing this, our work utilizes the Ag13@Ag16(BDT)12(TPP)4 (Ag29) nanocluster (where BDT represents 1,3‐benzenedithiol, and TPP is triphenylphosphine) as a template. We employ isotopic layering labeling, such as a109 Ag13@107 Ag16 core ‐shell structure, to mark the clusters. Subsequently, we conduct reactions with clusters featuring two different layering structures. Finally, we employ isotopic labeling to replace Ag in the shell, followed by analysis using ESI‐MS, enabling us to discern the process of intercluster reactions. We observed that the reactions primarily involve metal exchanges between the cores of different clusters and separately between their shells, highlighting distinct patterns of atomic‐level exchanges within these structures. This study thus offers pivotal insights into the molecular‐level mechanisms of metal exchange between clusters, significantly contributing to the development of metal nanocluster design and synthesis. [ABSTRACT FROM AUTHOR]

Triphenylmethyl‐based compounds such as rhodamines and fluoresceine representing an old and well‐known class of triphenylmethane dyes, are widely used in fluorescent labeling of bioimaging. Inspired by ultralong room temperature phosphorescence of triphenylphosphine derivatives, herein we report a methoxy substituted triarylmethanol ((4‐methoxyphenyl)diphenylmethanol, LJW‐1) exhibits ultralong room temperature phosphorescence (RTP) under ambient condition with afterglows of about 7 seconds. Its multiple C−H ⋅ ⋅ ⋅ π intermolecular interactions, C−H ⋅ ⋅ ⋅ O intermolecular interactions, hydrogen bond and π‐π interactions are beneficial for forming rigid environment in the aggregated state which is evidently an important factor in the appearance of excellent RTP. Different substituents on triarylmethanol result in compounds with different lifetimes varying from 7 μs to 818 ms. The substituent effects on the phosphorescence of triarylmethanol derivatives provide an efficient method for the design of organic RTP materials and may be enlightening the phosphorescence research of triarylmethanol derivatives. [ABSTRACT FROM AUTHOR]

The synthesis and isolation of a bismuth‐based analogue of the venerable triphenylphosphine oxide (Ph3PO) has remained a chimera to synthetic chemists for many years, due to its predicted high reactivity and instability. Through the hydrolysis of a cationic fluorotriarylbismuthonium(V) salt, we report here the isolation of unique hydroxytriarylbismuth(V) complexes, which served as precursor for the formation of the elusive monomeric triarylbismuthine oxide Dipp3Bi=O. Combined spectroscopic, crystallographic and computational studies provided insight into the bonding situation of the first monomeric triorganobismuth oxide complex. The Dipp3Bi=O and Mes3BiO⋅LiBArF complex exhibits O‐atom transfer reactivity, an uncommon reactivity feature for Ar3Pn=O. [ABSTRACT FROM AUTHOR]

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

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 literature data on the use of triphenylphosphine in determining peroxide functional groups and individual oxygen-containing compounds in the composition of the products of oxidation reactions of organic compounds with molecular oxygen and/or peroxides were systematized and discussed. The causes and mechanisms of distortions of the results of analytical determinations were identified and possible ways of their elimination were suggested. [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]

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]

Precise modification of a chemical site in a molecule at the single-atom level is one of the most elegant yet difficult transformations in chemistry. A reagent specifically designed for chemoselective introduction of monoatomic carbon is a particularly formidable challenge. Here, we report a straightforward, azide-free synthesis of a crystalline and isolable diazophosphorus ylide, Ph3PCN2, a stable compound with a carbon atom bonded to two chemically labile groups, triphenylphosphine (PPh3) and dinitrogen (N2). Without any additives, the diazophosphorus ylide serves as a highly selective transfer reagent for fragments, including Ph3PC, to deliver phosphorus ylide–terminated heterocumulenes and CN2 to produce multisubstituted pyrazoles. Ultimately, even exclusive carbon-atom transfer is possible. In reactions with aldehydes and acyclic and cyclic ketones (R2C=O), the carbon-atom substitution forms a vinylidene (R2C=C:) en route to alkynes or butatrienes. [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]

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]

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]

An expedient, green, practical, and vastly efficient three-component cyclo-condensation is catalyzed by triphenylphosphine. The 4-arylideneisoxazol-5(4H)-one heterocycles are generated in good to excellent isolated reaction yields. Experiments show that the best results were obtained using 15 mol% of the catalyst under aqueous conditions at room temperature. The sonochemical synthesis of 4-arylideneisoxazol-5(4H)-one derivatives were also performed by using 10 mol% of triphenylphosphine in water as an eco-friendly reaction medium. In the comparative method, ultrasonication showed shorter reaction times and also requires smaller amounts of catalyst. While aryl/heteroaryl aldehydes were used, the variation of β-keto-ester was also explored. The β-keto-esters (ethyl acetoacetate/ethyl 4-chloro-3-oxobutanoate/ethyl 3-oxohexanoate) under optimized reaction conditions reacted well and afforded the corresponding 4-arylideneisoxazol-5(4H)-ones in shorter reaction times. The approach is simple, approximately compatible with the pot-, atom-, and step-economy. [ABSTRACT FROM AUTHOR]

Organic radical luminescent materials have attracted worldwide attention because of their absolute spin‐allowed radiative transition and sensitivity to the environment, which give it multiple stimulus response properties. Nowadays, how to regulate and utilize the sensitivity of radicals has become a hot and difficult issue. Here, arylphosphonium bromide salts are introduced into the molecular backbone of naphthimide (NMI) using an intramolecular counterion strategy, and prepared a novel multifunctional stabilized radical luminescent: TPP‐o‐3OMe‐NMI‐Br. Interestingly, this molecule exhibits different assembly modes in different solvents, resulting in the generation of two crystals with different fluorescence (green: G‐C; orange–yellow: Y‐C), in which the Y‐C crystalline powder exhibits excellent stabilization properties for doublet and triplet excitons, which induce the emission of orange–yellow radical afterglow, and exhibits multi‐stimuli responsiveness to external pressure (P), temperature (T) and water (W). Moreover, interesting time‐dependent photoactivated colorful fluorescence and orange–yellow radical afterglow can be observed in TPP‐o‐3OMe‐NMI‐Br@PMMA films with different doping ratios and exhibit multi‐color tunability, multiple stimulus responses, multiple data encryption, and optical information erase/write behavior. This study not only broadens the types and applications of organic radical long afterglow materials but also provides new ideas for designing new organic "chameleon" luminescent materials in the field of smart luminescence materials. [ABSTRACT FROM AUTHOR]

A phosphine‐mediated cyclization of benzo[c][1,2]dithiol‐3‐ones and amidines is demonstrated herein. Triphenylphosphine was harnessed as the activating reagent to facilitate the ring‐opening of benzo[c][1,2]dithiol‐3‐ones via S−S bond cleavage. This PPh3‐Promoted cyclization reaction of benzo[c][1,2]dithiol‐3‐ones enabled to forge a diverse array of 1,3‐benzothiazones in decent yields with wide substrate scope under mild conditions. [ABSTRACT FROM AUTHOR]

This article discusses a new method for synthesizing 5-dialkylamino-1,2,4-oxadiazoles, which are important in drug discovery. The method involves using tertiary amines as temporary masked secondary amines, allowing for the direct construction of these compounds in a one-pot manner. The research provides a more efficient and facile approach for synthesizing these compounds, which have potential therapeutic applications. The article also provides detailed information on the synthesis and characterization of various N,N-dialkylamino-substituted 1,2,4-oxadiazoles, as well as piperazine-linked 1,2,4-oxadiazoles. The research was conducted at Chiang Mai University in Thailand and is supported by the university. [Extracted from the article]

A simple, one-pot synthesis of 3-(triphenyl phosphoranylidene) propanoate derivatives has been achieved in moderate to good yields via a multi-component reaction of triphenylphosphine and propylate using CuFe2O4@MIL-101(Fe) nanoparticle at room temperature conditions. The structure of the prepared nanocomposite was confirmed by energy dispersive X-ray spectroscopy (EDX), scanning electron microscopic analysis (SEM), X-ray diffraction (XRD), thermal gravimetry (TGA), and pore size distribution. The catalyst can be recovered magnetically and reused at least four times without significant loss of activity. Our approach demonstrates facile preparation using simple and readily available precursors, with catalysis occurring with good to high yields. This method has advantages in that the reactions are carried out under normal conditions and at room temperature, and the materials are mixed without purification and activation. [ABSTRACT FROM AUTHOR]

A stable dialkylgermanone was generated by mixing a solid of the corresponding dialkylgermylene and gaseous N2O. While the dialkylgermanone is marginally persistent in solution and gradually converts to its head‐to‐tail dimer at room temperature, the addition of THF to the dialkylgermanone provided an isolable THF‐coordinated dialkylgermanone. The THF‐coordinated dialkylgermanone reacts with H2O, THF, and B(C6F5)3 similar to the corresponding base‐free two‐coordinate dialkylsilanone. The dialkylgermanone undergoes deoxygenation in the presence of triphenylphosphine to provide the corresponding germylene and olefination upon treatment with phosphaylide Ph3PCHPh to afford the corresponding Ge=C bond compound (germa‐Wittig reaction). [ABSTRACT FROM AUTHOR]

A novel one-pot protocol that enables sequential execution of an aza-Piancatelli rearrangement and a Conia-ene type reaction has been developed under Lewis acid catalysis. Here, a combination of B(C6F5)3 and Cu(OTf)2, triethylamine, and triphenylphosphine yielded a wide range of cis-fused cyclopentenone-pyrrolidine scaffolds in one pot with good yields and diastereoselectivity. [ABSTRACT FROM AUTHOR]

The transient electron donor–acceptor (EDA) complex has been an emerging area in the photoinduced organic synthesis field, generating radicals without exogenous transition‐metal or organic dye‐based photoredox catalysts. The catalytic platform to form suitable photoactive EDA complexes for photochemical reduction reactions remains underdeveloped. Herein, a general photoinduced reductive alkylation via the EDA complex strategy is described. A simple yet multifunctional system, triphenylphosphine and iodide salt, promotes the photoinduced decarboxylative hydroalkylation, and reductive defluorinative decarboxylative alkylation of trifluoromethyl alkenes, to access trifluoromethyl alkanes and gem‐difluoroalkenes. Moreover, decarboxylative hydroalkylation can be applied to more kinds of electron‐deficient alkenes as a general Giese addition reaction. [ABSTRACT FROM AUTHOR]

An efficient reaction between triphenylphosphine or triphenyl phosphite and 2-oxoindoline-3-ylidene derivatives in the presence of acetylenic esters leads to functionalized 2-oxoindoline-3-ylidene containing phosphorus ylieds or phosphonate esters. All compounds obtained in these reactions are stable and have good yields. [ABSTRACT FROM AUTHOR]

C51H33F18O8P2Sm, monoclinic, P21/c (no. 14), a = 12.8193(9) Å, b = 13.4721(8) Å, c = 30.280(2) Å, β = 91.227(3)°, V = 5,228.2(6) Å3, Z = 4, Rgt(F) = 0.0370, wRref(F2) = 0.1025, T = 100.0 K. [ABSTRACT FROM AUTHOR]

[Display omitted] 1-Alkyl-3-phenylprop-2-yn-1-ones smoothly react with aromatic aldehydes in the presence of triphenylphosphine (acetonitrile, room temperature, 24 h) to regio- and stereo- selectively afford (Z)-2-benzylideneoxacyclopentan-3-ones in yields up to 93%. The proposed mechanism for the transformation involves 1,3- H proton shift from the alkyl group at the intermediate β-phosphoniovinylide species. [ABSTRACT FROM AUTHOR]

A strategy for sulfonylation of boronic acids with sulfonyl chlorides has been established via Suzuki‐type radical cross‐coupling. This approach allows for the synthesis of more than 50 sulfone examples enabled by photoredox catalysis under visible light radiation. Moreover, the title reaction is applied in late‐stage functionalization of bioactive molecules, and further transformation of the resulting sulfones into 2‐functionalized sulfones, borates, triphenylphosphine oxide and N‐arylcarbazole can be also achieved. [ABSTRACT FROM AUTHOR]

Amide bond is a ubiquitous and crucial functional group that serves as the linchpin for constructing proteins, peptides, and is also the central site in numerous drug molecules. Consequently, it is crucial to investigate the strategies and mechanisms of amidation reactions. In recent years, the use of electrochemistry for amidation has gained significant attention due to its exceptional qualities such as increased selectivity and eco-friendliness. However, due to the complexities of the reaction processes and the scarcity of relevant analytical tools, the studys of in-situ monitoring and mechanistic investigations on these electrochemical amidation reactions are rare. In response to this challenge, a novel coupling device was designed in this study. The main component of the coupling device was a glass capillary tube with a metal cover. The metal coating on the tip's outer surface was connected to a high voltage power supply to drive the electrospray ionization process. Additionally, the metal coating inside the tip was also connected to the metal coating on the tip's outer surface and served as the working electrode for an electrochemical reaction. When high voltage was applied, both the electrospray process and the electrochemical reaction on the tip could be driven simultaneously. The substances produced by the electrochemical reaction in the capillary tip could be quickly transfered to spray droplets, ionized via desolvation process, and finally detected via mass spectrometry. Based on this technique, a series of aromatic primary amines amidation reactions were observed in situ while using triphenylphosphine as the condensing agent. Numerous important intermediates were also discovered during these reactions. Remarkably, this novel approach not only facilitated continuous real-time monitoring of these reactions but also empowered scientists to unambiguously identify an array of key intermediates, including the elusive short-lived free radical intermediates. The electrochemical-mass spectrometry coupling device has numerous advantages, including short analysis delays, the ethical use of sample resources, and uncomplicated, simple preparation processes. It's potential to revolutionize the field of electroorganic synthesis reactions. This cutting-edge technique is poised to become an invaluable tool for rapid screening and in-depth investigations into the complex mechanisms of driving amidation reactions. The coupling device represents an exciting improvement forward in the context of drug investigations, where precision and efficiency are critical. Additionally, as society places increasing emphasis on environmental sustainability and the demand for precise chemical processes intensifies, this breakthrough coupling device is expected to become a formidable instrument in investigating the mechanism of electrochemical reactions. [ABSTRACT FROM AUTHOR]

In order to increase the catalytic activity of the Pd(II)-complexes in the alcoxycarbonylation of 1-olefins, the presence in solution of a strong Brönsted acid together with a phosphine ligand is usually required. From an industrial point of view, such two additives, however, influenced the sustainability of the process mainly caused by the related corrosion of the reaction vessel and the toxicity of the phosphine ligand. In this paper, the methoxycarbonylation of 1-octene has been efficiently carried out by using the [Pd(TsO)2(PPh3)2]/FeCl3 catalyst system. The catalyst is very active also without addition of PPh3, reaching the TON of ca. 1300 (mol/mol) in 2 hours by using the Fe(III)/Pd(II) = 400/1 (mol/mol) system. Such value is higher than the values obtained by using the traditional strong Brönsted acid TsOH or other Lewis acid such as AlCl3, in the presence of PPh3. The reaction takes place with the formation of two isomeric products of linear and branched structures with a yield towards the linear isomer of ca. 80%. [ABSTRACT FROM AUTHOR]

A simple one-pot preparation of (2,4,6-Trimethylbenzoyl)diphenylphosphine oxide (TPO) by employing the low-cost triphenylphosphine oxide (Ph3PO) as the starting material was described. Reaction with trimethylsilyl chloride (TMSCl) that transforms the intermediate sodium diphenylphosphonite (Ph2PONa) into (trimethylsilyl)oxy)diphenylphosphine (Ph2POTMS) is the key for the high yield of TPO. The reactions of Ph2PONa with other silyl chlorides are discussed. [ABSTRACT FROM AUTHOR]

A metal‐free one‐pot process for the gem‐difluoroolefination of amides is described. The reaction is based on interaction of generated in situ α‐chloroiminium salts with difluorinated phosphorus ylide formed from difluorocarbene and triphenylphosphine. The olefination involves nucleophile‐assisted dephosphorylation and proceeds within one hour at low temperature. The gem‐difluoroenamines were used in further transformations leading to a variety of fluoroalkylated amines. [ABSTRACT FROM AUTHOR]

[Display omitted] • P = Se active site organic compound was applied in the aluminum ion battery. • The ion mainly reacting with TP-Se in the aluminum ion battery is AlCl 2 +. • It has a specific capacity of 180.6 mAh g−1 and stable cycling for up to 1000 cycles. Due to their high reactivity and theoretical capacity, chalcogen elements have been favored and applied in many battery studies. However, the high surface charge density and high solubility of these elements as electrode materials have hindered their deeper exploration due to the shuttle effect. In this article, organic structural triphenylphosphine is used as a molecular main chain structure, and chalcogen elements O, S, and Se are introduced to combine with P as active sites. This approach not only takes advantage of the beneficial effects of the aromatic ring on the physical and chemical properties of the chalcogen element but also allows for the optimization of its advantages. By utilizing Triphenylphosphine selenide (TP-Se) as the cathode material in aluminum-ion batteries(AIBs), a high-performance Al-organic battery was fabricated, which exhibited a high initial capacity of 180.6 mAh g−1 and stable cycling for up to 1000 cycles. Based on density functional theory (DFT) calculations, TP-Se exhibits a smaller energy gap, which renders it favorable for chemical reactions. Moreover, the calculated results suggest that TP-Se tends to undergo redox reactions with AlCl 2 +. The molecular structure of triphenylphosphine and its combination with Se offers an enticing pathway for designing cathode materials in aluminum-organic batteries. [ABSTRACT FROM AUTHOR]

Eight new copper(I) triphenylphosphine complexes of bulky 5‐substituted‐2‐iminopyrrolyl ligands [Cu{κ2N,N′‐5‐R‐NC4H2–2‐C(H) = N(2,6‐iPr2C6H3)}(PPh3)n] (for n = 2: R = 2,6‐Me2C6H3 (1), 3,5‐(CF3)2C6H3 (2); for n = 1: R = 2,4,6‐iPr3C6H2 (3), CPh3 (4), 2,6‐(OMe)2C6H3 (5), 2,4,6‐Ph3C6H2 (6), 2,6‐Me2C6H3 (7), 3,5‐(CF3)2C6H3 (8)) are presently reported. The complexes were prepared in good yields by: (1) the reaction of the previously reported binuclear complexes [Cu{κN,κN'‐5‐R‐NC4H2‐2‐C(H) = N(2,6‐iPr2C6H3)}]2 (D1–D6) with triphenylphosphine (PPh3); (2) the reaction of the respective 5‐R‐2‐iminopyrrolyl potassium salts (KL1–KL3 and KL5) and [Cu(NCMe)2(PPh3)2]BF4; or (3) the abstraction of one PPh3 ligand present in complexes 1 and 2 with one equivalent of tris(pentafluorophenyl)borane (only for complexes 7 and 8, respectively). All complexes were characterized by NMR spectroscopy, elemental analysis and, in selected cases, by single crystal X‐ray diffraction. The single crystal X‐ray diffraction structures of 1, 3, and 5–7 displayed tetrahedral (for 1) and trigonal planar (for 3 and 5–7) coordination geometries. All complexes catalyzed the 1,4‐hydroboration of some α,β‐unsaturated (E)‐2‐enals with pinacolborane (HBPin), with 1,4:1,2‐addition selectivities as high as 29:1, the maximum turnover frequencies being equal to 9.9 min−1, and the 1,4‐hydroboration selectivity being favored by increasing steric protection of the 5‐substituted‐2‐iminopyrrolyl scaffold. Additionally, these complexes also catalyzed the hydroboration of an array of other aldehydes, reaching TOFs as high as 9.9 min−1. A combination of control experiments suggests that the catalyst system operates via a non‐classical copper‐hydride outer sphere route. [ABSTRACT FROM AUTHOR]

A novel heteroleptic Ag(I) compound, formulated as [AgL(PPh3)]BF4 (1) (where L represents 2,9-bis((E)-4-methoxystyryl)-1,10-phenanthroline and PPh3 stands for triphenylphosphine), was successfully synthesized and thoroughly characterized. The compound's stability in solution was confirmed through 1D and 2D nuclear magnetic resonance (NMR). The photo-irradiation of the complex in a CDCl3 solution, utilizing a common portable UV lamp emitting at λ = 365 nm, led to the partial transformation of the E,E-geometric isomer to E,Z, ultimately yielding a 1:1.4 molar ratio of isomers. Its molecular structure was determined via X-ray crystallography, while molecular packing was assessed using Hirshfeld calculations. The most notable interactions (51%) within the cationic inner sphere involved H···H bonds. The photophysical characteristics of the complex and L were evaluated both in the solid state and in solution (dichloromethane). Compound 1 is a weak emitter, with photoluminescence quantum yields of 8.6% and 4.3% in solution and the solid state, respectively. [ABSTRACT FROM AUTHOR]

Poor responses to medical care and the failure of pharmacological treatment for many high-frequency diseases, such as cancer and viral infections, have been widely documented. In this context, numerous metal-based substances, including cisplatin, auranofin, various gold metallodrugs, and ruthenium complexes, are under study as possible anticancer and antiviral agents. The two Ru(III) and Ru(II) complexes, namely, BOLD-100 and RAPTA-C, are presently being studied in a clinical trial and preclinical studies evaluation, respectively, as anticancer agents. Interestingly, BOLD-100 has also recently demonstrated antiviral activity against SARS-CoV-2, which is the virus responsible for the COVID-19 pandemic. Over the last years, much effort has been dedicated to discovering new dual anticancer–antiviral agents. Ru-based complexes could be very suitable in this respect. Thus, this review focuses on the most recent studies regarding newly synthesized Ru(II) complexes for use as anticancer and/or antiviral agents. [ABSTRACT FROM AUTHOR]

Allylbenzenes (apiol, dillapiol, myristicin and allyltetramethoxybenzene) are individual components of plant essential oils that demonstrate antitumor activity and can enhance the antitumor activity of cytotoxic drugs, such as paclitaxel, doxorubicin, cisplatin, etc. Triphenylphosphine (PPh3) derivatives of allylbenzenes are two to three orders of magnitude more potent than original allylbenzenes in terms of IC50. The inhibition of efflux pumps has been reported for allylbenzenes, and the PPh3 moiety is deemed to be responsible for preferential mitochondrial accumulation and the depolarization of mitochondrial membranes. However, due to poor solubility, the practical use of these substances has never been an option. Here, we show that this problem can be solved by using a complex formation with cyclodextrin (CD-based molecular containers) and polyanionic heparin, stabilizing the positive charge of the PPh3 cation. Such containers can solubilize both allylbenzenes and their PPh3 derivatives up to 0.4 mM concentration. Furthermore, we have observed that solubilized PPh3 derivatives indeed work as adjuvants, increasing the antitumor activity of paclitaxel against adenocarcinomic human alveolar basal epithelial cells (A549) by an order of magnitude (in terms of IC50) in addition to being quite powerful cytostatics themselves (IC50 in the range 1–10 µM). Even more importantly, CD-solubilized PPh3 derivatives show pronounced selectivity, being highly toxic for the A549 tumor cell line and minimally toxic for HEK293T non-tumor cells, red blood cells and sea urchin embryos. Indeed, in many cancers, the mitochondrial membrane is more prone to depolarization compared to normal cells, which probably explains the observed selectivity of our compounds, since PPh3 derivatives are known to act as mitochondria-targeting agents. According to the MTT test, 100 µM solution of PPh3 derivatives of allylbenzenes causes the death of up to 85% of A549 cancer cells, while for HEK293T non-cancer cells, only 15–20% of the cells died. The hemolytic index of the studied substances did not exceed 1%, and the thrombogenicity index was < 1.5%. Thus, this study outlines the experimental foundation for developing combined cytostatic medications, where effectiveness and selectivity are achieved through decreased concentration of the primary ingredient and the inclusion of adjuvants, which are safe or practically harmless substances. [ABSTRACT FROM AUTHOR]

Ph3P is found to be inert to sodium in toluene even on heating. This phenomenon leads to the finding that in toluene Ph3PS reacts with sodium efficiently and selectively to produce quantitative yields of highly valuable Ph3P and anhydrous Na2S. By applying this finding, anhydrous Na2S can be safely and conveniently prepared using a Ph3P-mediated reaction from sodium and sulfur. This finding also leads to the establishment of a feasible alternative strategy (the sulfur method) for the restoration of the Ph3PO waste to Ph3P that is greener and safer than the currently operating "chlorine method" using phosgene. [ABSTRACT FROM AUTHOR]

An electrochemical deoxygenative homo-coupling of aromatic aldehydes is achieved to selectively access bibenzyl and stilbene derivatives. The protocol allows the homo-coupling of aldehydes to occur after single-electron-reduction at the cathode. Taking advantage of the oxophilicity of triphenylphosphine, the electrochemical deoxygenation proceeds smoothly to give reductive homo-coupling products. [ABSTRACT FROM AUTHOR]

A new tripodal polytopic O,N-ligand on a triphenylphosphine oxide platform containing 2-pyridylmethyl groups in side fragments and also complexes of this ligand with lanthanum and uranyl cations were synthesized. The composition and structure of the obtained compounds were determined by elemental analysis, vibrational and multinuclear (1H, 13C, and 31P) NMR spectroscopy, and X-ray diffraction analysis. [ABSTRACT FROM AUTHOR]

A convenient approach towards previously unknown phosphonium salts containing a non-aromatic 2H-imidazole moiety is reported. The approach is based on a direct nucleophilic C(sp2)-H functionalization of 2H-imidazole 1-oxides with triphenylphosphine acting as a nucleophile. Herewith, the heterocyclic N-oxide moiety is utilized as an auxiliary group contributing to an abstraction of C-H proton during the elimination process. Newly obtained compounds can be a subject of further modification, e.g. used for the synthesis of monodeuterated 2H-imidazoles. [ABSTRACT FROM AUTHOR]

Keywords: coumarin; triphenylphosphine; hydroxylammonium chloride; proton transfer process; intramolecular cycloaddition; five-membered hetarene N -oxides EN coumarin triphenylphosphine hydroxylammonium chloride proton transfer process intramolecular cycloaddition five-membered hetarene N -oxides 3272 3280 9 09/29/23 20231018 NES 231018 Graph The nitrogen heterocycle is one of the most prevalent and valuable structural scaffolds in modern organic chemistry. SP 1 sp H NMR (500.13 MHz, DMSO- I d i SB 6 sb ): = 2.53 (s, 3 H, Me), 3.65 (s, 3 H, OMe), 4.14 (br s, 2 H, CH SB 2 sb ), 7.20 (d, SP 3 sp I J i SB HH sb = 8.8 Hz, 1 H, CH6 of coumarin), 7.41 (d, SP 3 sp I J i SB HH sb = 8.7 Hz, 1 H, CH7 of coumarin), 7.80 (s, 1 H, CH9 coumarin), 12.06 (br s, 1 H, OH). SP 1 sp H NMR (300.13 MHz, DMSO- I d i SB 6 sb ): = 2.53 (s, 3 H, Me), 3.62 (s, 3 H, OMe), 4.10 (br s, 2 H, CH SB 2 sb ), 7.19 (t SP 3 sp I J i SB HH sb = 7.5 Hz, 1 H, CH8 of coumarin), 7.23 (d, SP 3 sp I J i SB HH sb = 7.4 Hz, 1 H, CH6 of coumarin), 7.27 (t SP 3 sp I J i SB HH sb = 7.9 Hz, 1 H, CH7 of coumarin), 7.70 (d, SP 3 sp I J i SB HH sb = 7.6 Hz, 1 H, CH9 coumarin), 12.10 (br s, 1 H, OH). SP 1 sp H NMR (500.13 MHz, DMSO- I d i SB 6 sb ): = 2.54 (s, 3 H, Me), 3.65 (s, 3 H, OMe), 4.16 (br s, 2 H, CH SB 2 sb ), 7.26 (d, SP 3 sp I J i SB HH sb = 8.8 Hz, 1 H, CH6 of coumarin), 7.30 (d, SP 3 sp I J i SB HH sb = 8.9 Hz, 1 H, CH7 of coumarin), 7.70 (s, 1 H, CH9 coumarin), 12.05 (br s, 1 H, OH). [Extracted from the article]

All aromatic C–H bonds of triphenylphosphine (PPh3) were efficiently replaced by C–D bonds using Ru/C and Ir/C co-catalysts in 2-PrOH and D2O, an inexpensive deuterium source. Furthermore, non-radioactive and safe deuterium-incorporated Mito-Q (drug candidate) was prepared from deuterated PPh3 and used for the live-cell Raman imaging to evaluate the mitochondrial uptake. [ABSTRACT FROM AUTHOR]

Sulfonyl chlorides are a class of cheap and readily available basic chemicals, which have routinely served as electrophilic reagents in their chemical transformations. Herein, we disclose a novel PPh3‐mediated nucleophilic sulfonation method of sulfonyl chlorides with arynes. Different from the classical P(III)‐mediated reductive deoxygenation reaction of sulfonyl chlorides, the valence state of the sulfur atom has not been changed. This protocol exhibits broad functional group tolerance and provides a direct approach to a variety of aryl and alkyl sulfones. [ABSTRACT FROM AUTHOR]

The reaction between CpRu(PPh3)2NCS (1a) and PMePh2 yields CpRu(PPh3)(PMePh2)NCS (2a) while CpRu(PPh3)(PMePh2)Cl reacts with SCN− to form the S-bonded isomer, CpRu(PPh3)(PMePh2)SCN (2b). Compound 1a and the linkage isomers of 2 were characterized by X-ray crystallography. The kinetics of the reaction between 1a and PMePh2 under pseudo-first order conditions in THF and in fluorobenzene to form 2a are consistent with a dissociative interchange mechanism. Activation parameters for the reaction are: ΔH† = 15.7 ± 0.6 kcal mol−1 and ΔS† = –35 ± 2 cal mol−1 K−1 in THF vs. ΔH† = 24.8 ± 1.2 kcal mol−1 and ΔS† = –6 ± 4 cal mol−1 K−1 in C6H5F. In the presence of added SCN−, the rate of phosphine substitution is unchanged but a mixture of 2a and 2b is observed. The selenocyanate derivative, CpRu(PPh3)2SeCN (3b), crystallizes as the Se-bonded linkage isomer. Compound 3b reacts with PMePh2 under pseudo-first order conditions in fluorobenzene to form CpRu(PPh3)(PMePh2)SeCN (4b) at a much faster rate than 1a with activation parameters: ΔH† = 30.9 ± 4.8 kcal mol−1 and ΔS† = 22.4 ± 15.9 cal mol−1 K−1 with no evidence for linkage isomerization to the N-bonded products. [ABSTRACT FROM AUTHOR]

In this study, a series of ladder‐like polysiloxanes are synthesized by introducing double‐chain Si–O–Si polymer as the backbone and the carbazole and triphenylphosphine oxide with high triplet energy as side groups. The ladder‐like structures of polysiloxanes are achieved through a controlled polymerization method that involves the monomer self‐assembly and subsequent surface‐restricted solid‐phase in situ condensation through freeze‐drying. The introduction of siloxane improves thermal stability of the polymers and inhibits the conjugation of the polymers between the side groups, leading to an increase in the triplet energy level. Therefore, all these polymers perform higher triplet energy levels than phosphorescent emitter (FIrpic). The cyclic voltammetry measurements demonstrate that the bipolar polymer exhibits a high highest occupied molecular orbital (HOMO) value of −5.32 eV, which is consistent with the work function of ITO/PEDOT:PSS, consequently facilitating hole injection. Furthermore, the incorporation of triphenylphosphine oxide promotes electron injection. Molecular simulations reveal that the frontier orbital distributions of the bipolar polymer are located on the carbazole and triphenylphosphine groups, respectively, which facilitate the transport of electrons and holes. [ABSTRACT FROM AUTHOR]