Triphenylphosphine Sulfide Research Articles

Spectroscopic and biological studies of Pd(II) complexes of 5-(p-tolyl)-1,3,4-oxadiazole-2-thiol

Reactions of Na2PdCl4 with two equivalents of 5-(p-tolyl)-1,3,4-oxadiazole-2-thiol (MoxSH), afford complex of the type [Pd(MoxS)2] (1). Further reaction with equivalent mole of diphosphine ligand {Ph2P(CH2)nPPh2} ( where n = 1 dppm, 2 dppe, 3 dppp, 4 dppb, (CH2)n = dppf ) or two equivalents of triphenyl phosphine or triphenyl phosphine sulfide affords mixed-ligand complexes of the type [Pd(MoxS)2(Ph2P(CH2)nPPh2)] (2-6), [Pd(MoxS)2(PPh3)2] (7) and [Pd(MoxS)2(SPPh3)2](8). The prepared complexes were characterized using different physical and spectroscopic methods. The results indicated that the MoxS ligand behave as coordinate in a anion monodentate fashion sulfur atom to give a square planer around the metal ion. Preliminary anti-bacterial activity has been assessed against Escherichia coli, Staphylococcus aureus, and Bacillus subtilis bacteria. The prepared complexes show good activity in compared with standard drug. [Pd(MoxS)2(dppf)] (6) displays good activity (18, 22 and 20 mm) against certain tested microbes Escherichia coli, Staphylococcus aureus and Bacillus subtilis, respectively. KEY WORDS: Complexes, Palladium, Thione, Anti-bacteria, Phosphine Bull. Chem. Soc. Ethiop. 2025, 39(1), 79-90. DOI: https://dx.doi.org/10.4314/bcse.v39i1.6

Yb/Si frustrated Lewis pairs with a labile naphthalenyl bridge.

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.

Activation of SF5CF3 by the N-Heterocyclic Carbene SIMes.

The greenhouse gas SF5CF3 was photochemically activated with SIMes (1,3-Bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene) to give 1,3-dimesityl-2,2-difluoroimidazolidine (SIMesF2), and 1,3-dimesitylimidazolidine-2-sulfide, as well as the trifluoromethylated carbene derivative 1,3-dimesityl-2-fluoro-2-trifluoromethylimidazolidine. CF3 radicals, as well as SF4, serve presumably as intermediates of the conversions. In addition, the photochemical activation of SF5CF3 was performed in the presence of triphenylphosphine. The formation of triphenyldifluorophosphorane and triphenylphosphine sulfide was observed.

Novel potentiometric carbon paste electrodes for trace detection of uranyl(II) ions in petroleum water samples

Two different phosphine sulfide derivatives have been explored as electroactive materials to modify carbon paste electrodes for the accurate detection of uranyl(II) ions. The optimized electrodes based on triphenylphosphine sulfide (L1) and triisobutylphosphine sulfide (L2) responded linearly towards uranyl(II) ions within the range of 1.0 × 10-7 – 1.0 × 10-1 M. Good sensitivity (29.32 ± 0.53 and 27.99 ± 0.61 mV per decade) and detection capability up to 7.9 × 10-8 and 1.0 × 10-7 M uranyl(II) were observed for L1- and L2-based electrodes, respectively. The effect of solution temperature on uranyl(II) determination was studied within 10–60 °C. Selectivity studies showed that the electrodes are capable to discriminate uranyl(II) ions over a large number of possible co-existing inorganic interferents. Moreover, they exhibited speedy response, thermal and long-term stability, and significant reusability. Petroleum water samples spiked with uranyl(II) ions were analyzed utilizing the developed electrodes where good recovery and accuracy were achieved, demonstrating the real-life applicability of the developed electrodes.

Elucidating mechanochemical reactivity of a ternary halogen-bonded cocrystal system by computational and calorimetric studies.

Discovery of a halogen-bonded ternary cocrystal of 1,3,5-trifluoro-2,4,6-triiodobenzene with pyrazine and triphenylphosphine sulfide has revealed a complex landscape of multicomponent phases, all achievable by mechanochemical interconversion. The observed solid-state reaction pathways were explained by periodic density-functional calculations and comprehensive intermolecular interaction analysis, supported by dissolution calorimetry measurements.

Convenient Synthesis of Triphenylphosphine Sulfide from Sulfur and Triphenylphosphine

Elemental sulfur (S8) was found to react very rapidly (<1 min) with a stoichiometric amount of triphenylphosphine at rt in sufficient amount of solvent (0.2–0.5 mL of solvent/1 mmol of PPh3). Compared to the previously described methods, the present procedure constitute excellent access to triphenylphosphine sulfide.

Synergistic coupling of P-doped Pd4S nanoparticles with P/S-co-doped reduced graphene oxide for enhanced alkaline oxygen reduction

Pd-based materials are promising alternatives to Pt for oxygen reduction reactions (ORR), which is the critical electrode reaction for many oxygen-electrocatalysis-based energy storage and conversion devices. Modification of electronic structure and support effect are powerful tools for boosting ORR performance of Pd-based catalysts. Herein, phosphorus (P) doped-palladium sulfide (Pd4S) nanoparticles decorated on P/sulfur (S) co-doped reduced graphene oxide (P-Pd4S/PSG) is prepared via a one-step solvothermal method using triphenylphosphine sulfide as both P and S sources. The incorporation of P effectively tailors the electronic structure and coordination environment of Pd4S, while P-Pd4S decorated on PSG generates strong metal-support interaction, which synergistically promotes electrocatalytic performance towards ORR. The proposed synthetic method offers a feasible route for the rational construction of heteroatoms-doped carbon − metal composites with high-performance for ORR and other potential energy applications.

Utilizing Co-Crystallization as a Tool to Unravel the Structural Diversity and Electronic Features of I···S Halogen Bonded Interactions in Stoichiomorphic Co-Crystals

In the current investigation, we report five new co-crystals formed by combinations of triphenylphosphine sulfide (PS) with 1,3,5-triiodo-2,4,6-trifluorobenzene (I3F), triphenylphosphine sulfide (P...

Quantitative UHPSFC-MS analysis of elemental sulfur in mineral oil via derivatisation with triphenylphosphine: application to corrosive sulfur-related power transformer failure.

An ultrahigh-performance supercritical fluid chromatography-mass spectrometry (UHPSFC-MS) method has been developed as a rapid and reliable analytical method for the detection and quantification of elemental sulfur in mineral transformer oil. The method described in this paper is based on the selective reaction of elemental sulfur with triphenylphosphine (TPP). The derivatisation of elemental sulfur requires minimal sample preparation and resulted in the formation of a single compound, namely triphenylphosphine sulfide (TPPS). This derivative is quantified from the complex oil composition using electrospray ionisation-mass spectrometry (ESI-MS) in selected ion monitoring (SIM) mode, and the reported UHPSFC-MS method allows detection and quantification of the derivative at ppb levels. As sulfur contamination in mineral transformer oil has been linked to costly failures of oil/paper-based power transformers due to corrosion, the analytical approach is demonstrated through its application to mineral oil samples from in service and decommisioned power transformers. The method is ideal as a routine test or to confirm the presence of elemental sulfur in samples where corrosion has occurred.

Phosphorus-triggered modification of the electronic structure and surface properties of Pd4S nanowires for robust hydrogen evolution electrocatalysis

Phosphorus-doped Pd4S nanowires were fabricated by treating pre-synthesized Pd nanowires with triphenylphosphine sulphide and demonstrated improved electrocatalytic hydrogen evolution.

Mononuclear copper(I) and binuclear silver(I) complexes of SPPh3 ligand: Synthesis, crystal structure, properties

Two new complexes, [Cu(SPPh3)3]2(PF6)2 (1) and [Ag2(SPPh3)2](PF6)2 (2), were prepared from [M(CH3CN)4](PF6)] (M = Cu and Ag) and triphenylphosphine sulfide ligand (SPPh3). The complexes have been characterized by elemental analysis, and UV-Vis and IR spectroscopies. Single-crystal X-ray structure analyses reveals that complexes 1 and 2 can both be described as a planar triangular configuration. Complex 1 is mononuclear and shows two crystallographically independent and chemically identical [Cu(SPPh3)3]+ cations. In binuclear complex 2, the sulfur atoms in SPPh3 adopt two different coordination modes, namely monodentate and monoatomic bridging. Luminescence properties investigation in solid state show that complex 1 revealed only one emission band at 471 nm (λex = 310 nm), which may be attributed to metal-to-ligand charge-transfer [MLCT]. However, complex 2 had two emission peaks which attributed to π–π* and n–π* transitions. Electrochemical experiment illustrated the complexes 1 and 2 represent irreversible Cu+/Cu2+ or Ag+/Ag pairs, respectively. In vitro antioxidant tests showed that the complex 2 had significant antioxidant activity against hydroxyl radicals.

Versatile Dibenzothio[seleno]phenes via Hexadehydro-Diels-Alder Domino Cyclization.

A facile strategy to synthesize highly substituted dibenzoselenophenes and dibenzothiophenes by a domino hexadehydro-Diels–Alder reaction is reported in this article. The formation of three new C–C bonds, one new Caryl–Se/Caryl–S bond, and C–H σ-bond migration via one-pot multiterminal cycloaddition reactions were involved in over three transformations. The target tetracyclic compounds were prepared from tetraynes with a triphenylphosphine selenide or triphenylphosphine sulfide. This reaction played a pivotal role in constructing natural thio[seleno]phene cores, which were highly substituted, and is a robust method for producing fused heterocycles.

A new cuprous coordinating polymer constructed by bridging 2,2-(1,4-butanediyl)bis-1,3-benzoxazole ligand: synthesis, structure, and properties

A new cuprous coordination polymer (CP) with 2,2-(1,4-butanediyl)bis-1,3-benzoxazole (BBO) and triphenylphosphine sulfide (SPPh3) ligands, {[Cu(BBO)(SPPh3)]ClO4}n (1), has been characterized by elemental analysis, UV-Vis, infrared spectra and single-crystal X-ray diffraction. The structural analysis revealed that 1 exhibits a one-dimensional CP and is in a three-coordinate slightly distorted trigonal planar environment in which the total angle around the copper(I) atom is 359.2°. Solid luminescence properties investigation showed that 1 had one emission peak at 428 nm (λex = 355 nm, blue luminescence), which may be attributed to MLCT [(d10(Cu)→π*]. The cyclic voltammogram of 1 represents irreversible Cu2+/Cu+ pairs. The antioxidant activity experiment shows that 1 has the potential ability to scavenge hydroxyl and superoxide radical in vitro studies.

Computational study and characteristics of In2S3 thin films: effects of substrate nature and deposition temperature

In this work, we investigate the effects of both growth temperature and substrate nature on different properties of indium sulfide thin films prepared by chemical vapor deposition method using triphenylphosphine sulfide as a sulfur precursor. The structural, morphological, and optical properties of the resulting thin films were characterized using x-ray diffraction, scanning electron microscopy (SEM) and UV–vis spectroscopy respectively. The structural study has proved that pure nanocrsytalline β-indium sulfide films were obtained at 300 and 400 °C regardless of the substrate nature, while higher growth temperature (500 °C) leads to the formation of pure indium oxide films. From the SEM images, it is derived that the surface morphology of the obtained films was independent to both growth temperature and substrate nature. The electronic structure of β-In2S3 was computed using density functional theory calculations. The optical properties of the obtained films such as energy band-gap, extinction coefficient, refractive index, dielectric constant and optical conductivity were investigated theoretically and experimentally. It was shown that these parameters were mainly controlled by the substrate type and the phase formed. The theoretical optical investigation was in full agreement with the experimental results. Oscillator energy, dispersion energy and Urbach energy were also estimated. Blue and violet PL emissions indicate the useful application of the obtained films as blue and violet light emitters.

Synthesis, crystal structure, fluorescence and electrochemical properties of two Ag(I) complexes based on 2-(4′-pyridyl)-benzoxazole/SPPh3 ligands

To explore the luminescence properties of silver complexes in the solid state, two Ag(I) complexes, [Ag(4-PBO)2(NO3)] {di[2-(4′-pyridyl)-benzoxazole]silver(I) nitrate} (1) and [Ag2(SPPh3)4](ClO4)2 {[tetra(triphenylphosphine sulfide)disilver(I)] diperchlorate} (2) (4-PBO =2-(4′-pyridyl)-benzoxazole, SPPh3 = triphenylphosphine sulfide), have been synthesized and characterized by elemental analysis, FT-IR and UV-Vis spectroscopy. Single-crystal X-ray diffraction revealed that 1 is three-coordinate by two nitrogen atoms from two 4-PBO ligands and an oxygen atom from the coordinated nitrate anion forming a triangular plane configuration. In 2, the SPPh3 ligands adopt a monodentate coordinated and monoatomic bridging mode to connect two Ag(I) ions, resulting in a three-coordinate symmetrical binuclear structure. In the solid state, the luminescence properties of the ligands 4-PBO, SPPh3 and their complexes were investigated. The results demonstrated that 1 results in the fluorescence quenching of aggregates due to the strong π–π stacking effect. The fluorescence enhancement of 2 may be attributed to the “aggregation-induced emission” (AIE) effect of restricted intramolecular rotations of the peripheral phenyl rings against the central core. In addition, cyclic voltammograms of 1 and 2 indicated an irreversible Ag+/Ag couple.

Electrophilic Bromolactonization of Cyclopropyl Diesters Using Lewis Basic Chalcogenide Catalysts

AbstractAn efficient and regioselective electrophilic bromolactonization of cyclopropylmethyl diesters using triphenylphosphine sulfide (Ph3PS) or diphenyl selenide (Ph2Se) as the Lewis basic chalcogenide catalyst has been developed. It was observed that Ph3PS favored the formation of anti‐diastereomer and yielded the multi‐functional γ‐lactones. Interestingly, the diastereoselectivity was reversed when using Ph2Se as a catalyst where the syn‐product instead of the anti‐product was favored.magnified image

Palladium-Catalyzed Functionalization of Kraft Lignin: Ether Linkages through the Telomerization Reaction.

Kraft lignin was efficiently functionalized with octadienyl ether linkages through the palladium-catalyzed telomerization of 1,3-butadiene. Comparison with molecular model substrates assessed the grafting of phenols and alcohols and an optimization study led to up to 69 % conversion of the total number of hydroxyl groups present in lignin. This catalytic study evidenced the partial oxidation of triphenylphosphine into triphenylphosphine oxide and triphenylphosphine sulfide by contaminants present in the industrial grade kraft lignin. The telomerised lignin is a malleable material and a preliminary study of the thermal properties showed a decrease in the glass transition in comparison with the starting material.

Cyclohexane-Coupled Bipolar Host Materials with High Triplet Energies for Organic Light-Emitting Diodes Based on Thermally Activated Delayed Fluorescence.

Thermally activated delayed fluorescence-based organic light-emitting diodes (TADF-OLEDs) have recently attracted tremendous research interest as next-generation optoelectronic devices. However, there are a limited number of host materials with an appropriately high lowest-excited triplet energy (ET) and bipolar charge transport properties for high-efficiency TADF-OLEDs. Moreover, these host materials should have high thermal and morphological stabilities. In this study, we develop novel bipolar host materials consisting of an electron-donating 9-phenylcarbazole unit and an electron-accepting triphenylphosphine oxide, triphenylphosphine sulfide, or 2,4,6-triphenyl-1,3,5-triazine unit linked by a nonconjugated cyclohexane core. These bipolar host materials possess high glass-transition temperatures of over 100 °C and high ET values of approximately 3.0 eV. TADF-OLEDs employing these bipolar host materials could achieve high external electroluminescence quantum efficiencies of up to 21.7% together with reduced efficiency roll-off characteristics, because of expansion of the charge-recombination zone within the emission layer arising from the bipolar charge transport ability of these host materials.

Structural and optical properties of tin (II) sulfide thin films deposited using organophosphorus precursor (Ph3PS)

Tin sulfide (SnS) thin films have been deposited onto glass substrates using triphenylphosphine sulfide (Ph3PS) as a sulfur precursor in a chemical vapor deposition reactor in a temperature range of 250 °C–400 °C. The influence of the sulphidisation temperature in the crystal structure, surface morphology, chemical composition and optical properties has been investigated. X-ray diffraction, energy dispersive analysis of x-rays, and Raman spectroscopy showed that pure SnS thin films have been successfully obtained at 250 °C. All the deposited films were polycrystalline and showed orthorhombic structure, with a preferential orientation according to the direction 〈111〉. The optical measurements showed that the films deposited exhibited a direct allowed transition and have a relatively high absorption coefficient. The presence of mixed tin sulfide phases granted by the variation of the sulphidisation temperature has affected the optical properties of the deposited films. The refractive index (n) and extinction coefficient (k), has low values compared to conventional semiconductor materials. The grown films can be considered as a good light absorbing material and a promising candidate for application in optoelectronic devices.

Triphenylphosphine sulfide-[C<sub>n</sub>mim][Tf<sub>2</sub>N]を用いた塩酸水溶液中における白金族元素の分配挙動

Although solvent extraction has been used in the recovery of rare metals from urban mines, some challenges remain. For example, large amounts of organic solvent are required for Pd (II) separation owing to the slow extraction kinetics of dihexylsulfide (DHS). This lengthens the separation process and increases the evaporation loss of diluents. In our previous work, we found that Pd (II) quickly separates from a hydrochloric acid medium using triphenylphosphine as a phosphorus-based extractant. In this work, we investigate the extraction and backextraction behavior of Rh (III), Pd (II), and Pt (IV) in a hydrochloric acid medium using the combination of triphenylphosphine sulfide (TPPS) and ionic liquids (ILs). Results show that the extraction mechanism of Pd (II) is based on the cooperative extraction effect of TPPS and ILs. Additionally, it was confirmed that the third phase during Pd (II) extraction was inhibited using TPPS-ILs. Furthermore, this study investigated the separation behavior of Rh (III), Pd (II), and Pt (IV) from a hydrochloric acid medium using TPPS-ILs as an extractant and a multiple back-extractant.