Phosphine Sulfide Research Articles

Synthesis and characterization of enantiopure planar-chiral phosphorus-linked diferrocenes.

In the course of an ongoing synthetic project on cyclic diferrocenylphosphines, we obtained a group of planar-chiral diferrocenyl compounds useful as precursors for subsequent cyclization. Here we report the crystal structures of two symmetric compounds [(FcA)2(Ph)P], one of which contains four stereogenic centres (two C chiral and two planar chiral centres), i.e. 1,1'-(phenylphosphanediyl)bis{(2Sp)-2-[(1R)-1-(acetyloxy)ethyl]ferrocene}, [Fe2(C5H5)2(C24H25O4P)], and the other phosphine sulfide is a purely planar-chiral compound (two planar chiral centres), i.e. bis[(2Sp)--2-ethenylferrocen-1-yl]phenylphosphane sulfide, [Fe2(C5H5)2(C20H17PS)]. Owing to the stereocentres present, reactions performed on [(FcA)2(Ph)P]-type compounds strongly favour one ferrocene unit over the other due to diastereoselectivity. Furthermore, we present four related structures where the ferrocene units are not identical [(FcA)(FcB)(Ph)P]. These are {(2Sp)-2-[(1R)-1-(acetyloxy)ethyl]ferrocen-1-yl}[(2Sp)-2-ethenylferrocen-1-yl]phenyl-(S)-phosphine sulfide, [Fe2(C5H5)2(C22H21O2PS)], [(2Sp)-2-ethenylferrocen-1-yl]{(2Sp)-2-[(1R)-1-hydroxyethyl]ferrocen-1-yl}phenyl-(S)-phosphine sulfide, [Fe2(C5H5)2(C20H19OPS)], {(2Sp)-2-[(1R)-1-(acetyloxy)ethyl]ferrocen-1-yl}{(2Sp)-2-[(1R)-1-hydroxyethyl]ferrocen-1-yl}phenyl-(R)-phosphine sulfide, [Fe2(C5H5)2(C22H23O3PS)], and {(2Sp)-2-[(1R)-1-benzylamino)ethyl]ferrocen-1-yl}[(2Sp)-2-ethenylferrocen-1-yl]phenyl-(S)-phosphine sulfide, [Fe2(C5H5)2(C27H26NPS)]. All of the structures are accessible in one step from known precursors.

Reaction Mechanism of Simultaneous Removal of H2S and PH3 Using Modified Manganese Slag Slurry

The presence of phosphine (PH3) and hydrogen sulfide (H2S) in industrial tail gas results in the difficulty of secondary utilization. Using waste solid as a wet absorbent to purify the H2S and PH3 is an attractive strategy with the achievement of “waste controlled by waste”. In this study, the reaction mechanism of simultaneously removing H2S and PH3 by modified manganese slag slurry was investigated. Through the acid leaching method for raw manganese slag and the solid–liquid separation subsequently, the liquid-phase part has a critical influence on removing H2S and PH3. Furthermore, simulation experiments using metal ions for modified manganese slag slurry were carried out to investigate the effect of varied metal ions on the removal of H2S and PH3. The results showed that Cu2+ and Al3+ have a promoting effect on H2S and PH3 conversion. In addition, the Cu2+ has liquid-phase catalytic oxidation for H2S and PH3 through the conversion of Cu(II) to Cu(I).

Fumigation Activity against Phosphine-Resistant Tribolium castaneum (Coleoptera: Tenebrionidae) Using Carbonyl Sulfide.

Simple SummaryPhosphine is one of the most widely used fumigants for the control of stored grain pests in quarantine. However, PH3 resistance to many stored pests has been reported. In this study, the fumigation activity of carbonyl sulfide was researched as an alternative fumigant to control PH3-resistant pests. In PH3 treatment, there was a clear difference in the fumigation activity of domestic strain Tribolium castaneum and resistance strain T. castaneum, but both the d- and r-strains of T. castaneum showed similar results in the carbonyl sulfide (COS) treatment. Furthermore, both PH3 and COS showed no significant difference in fumigation activity in Oryzaephilus surinamensis.Phosphine resistance is occurring among stored-grain pests worldwide. This study investigated the fumigation activity of phosphine (PH3) and carbonyl sulfide (COS) against domestic strain (d-strain) Tribolium castaneum, resistance strain (r-strain) T. castaneum and Oryzaephilus surinamensis. All developmental stages of the pests were exposed to two fumigants (PH3 and COS), and the fumigation activity according to the dose and exposure time was evaluated in a 12-L desiccator and 0.5 m3 fumigation chamber. The rice sorption rate and quality following exposure to thetwofumigants were evaluated. The mortality was 2.9% in r-strain T. castaneum, 49.5% in d-strain T. castaneum and 99.2% in O. surinamensis when 2 mg/L PH3 was used in a 12-L desiccator for 4 h. However, all pest developmental stages showed 100% mortality after 24 h of exposure in the 0.5 m3 fumigation chamber, except for the r-strain T. castaneum. A mortalityof 100% was observed in all of the r-strain T. castaneum developmental stages at an exposure time of 192 h. For COS applied at 40.23 mg/L and 50 g/m3 in the 12-L desiccator and the 0.5 m3 fumigation chamber, respectively, 100% mortality was observed across all developmental stages regardless of species and strain. The sorption of COS was 10% higher than that of PH3, but there was no significant difference in rice quality compared to that in the control. Therefore, this study suggests that COS can be used for controlling T. castaneum resistant to PH3.

Quantum Chemical Study of the Addition of Secondary Phosphine Chalcogenides to Vinyl Selenides

DFT quantum chemical calculations at the B3PW91/6-31G(d) level of theory have shown that the addition of secondary phosphine sulfides and phosphine selenides with alkyl, phenyl, and phenylalkyl substituents to pentyl vinyl and hexyl vinyl selenides follows a molecular mechanism against the Markovnikov rule through energetically favorable eight-membered transition state, leading to the formation of tertiary phosphine chalcogenides. Secondary phosphine selenides are more reactive than the corresponding phosphine sulfides.

Phosphine Sulfides: New Aspects of Organophosphorus Compounds

Abstract Phosphine sulfides are the pentavalent derivatives of organophosphines and are usually used as synthetic intermediates of organophosphines for their isolation as protected analogs because of the stability toward oxidation. Recently, several applications of phosphine sulfides have been disclosed as functional materials, organocatalysts, ligands, and extractants. In addition, several synthetic uses of phosphine sulfides have also developed, in which the thiophosphinyl group plays an essential role. This Highlight Review covers recent applications and syntheses of organophosphine sulfides.

Synthesis of nitrogen, phosphorus, selenium and sulfur-containing heterocyclic compounds – Determination of their carbonic anhydrase, acetylcholinesterase, butyrylcholinesterase and α-glycosidase inhibition properties

Sulfur-containing pyrroles (1–3), tris(2-pyridyl)phosphine(selenide) sulfide (4–5) and 4-benzyl-6-(thiophen-2-yl)pyrimidin-2-amine (6) were synthesized and characterized by elemental analysis, IR and NMR spectra. In this study, the synthesized compounds of nitrogen, phosphorus, selenium and sulfur-containing heterocyclic compounds (1–6) were evaluated against the human erythrocyte carbonic anhydrase I, and II isoenzymes, acetylcholinesterase (AChE), butyrylcholinesterase (BChE), and α-glycosidase enzymes. The synthesized heterocyclic compounds showed IC50 values in range of 33.32–60.79 nM against hCA I, and 37.05–66.64 nM against hCA II closely associated with various physiological and pathological processes. On the other hand, IC50 values were found in range of 13.13–22.21 nM against AChE, 0.54–31.22 nM against BChE, and 13.51–26.55 nM against α-glycosidase as a hydrolytic enzyme. As a result, nitrogen, phosphorus, selenium and sulfur-containing heterocyclic compounds (1–6) demonstrated potent inhibition profiles against indicated metabolic enzymes. Therefore, we believe that these results may contribute to the development of new drugs particularly in the treatment of some global disorders including glaucoma, Alzheimer’s disease and diabetes.

A Sensitive Impedimetric Sensor Based on Biosourced Polyphosphine Films for the Detection of Lead Ions

In this work, impedimetric sensors were developed for the detection of the four WFD heavy metals Pb2+, Cd2+, Hg2+ and Ni2+, by the modification of a gold electrode with four partially biosourced polyphosphine polymers. These polymers were obtained with satisfactory yields by polycondensation of the bis(4-fluorophenyl)(4-methylphenyl)phosphine sulfide and the bis(4-fluorophenyl)(4-methylphenyl)phosphine oxide using isosorbide or bisphenol A. The chemical structures and number-average molecular weights of the resulting polymers were determined by NMR spectroscopy (1H, 19F, and 31P) and by size exclusion chromatography. Glass transition temperatures varied between 184 and 202 °C depending on the composition of polymers. The bio-based poly(etherphosphine) oxide modified sensor showed better analytical performance than petrochemical based oxide for the detection of Pb2+. A detection limit of 10−10 g/L or 0.5 pM, which is 104 times lower than that of the anodic stripping voltammetric and the potentiometric sensors. A reversibility is obtained through rinsing of the impedimetric sensor with an EDTA solution.

Rapid Synthesis of Chiral 1,2-Bisphosphine Derivatives through Copper(I)-Catalyzed Asymmetric Conjugate Hydrophosphination.

1,2-Bisphosphines have been identified as one class of important and powerful chiral ligands in asymmetric catalysis with transition metals. Herein, a copper(I)-catalyzed asymmetric hydrophosphination of α,β-unsaturated phosphine sulfides was developed with the assistance of "soft-soft" interaction between copper(I)-catalyst and the phosphine sulfide moiety, which afforded 1,2-bisphosphine derivatives with diversified electronic nature and steric hindrance in high to excellent yields with high to excellent enantioselectivity. Moreover, the challenging catalytic asymmetric hydrophosphination/protonation reaction was achieved with excellent enantioselectivity. Strikingly, the dynamic kinetic resolution of racemic diarylphosphines was also successfully carried out with high to excellent diastereo- and enantioselectivities. Interestingly, the nucleophilic copper(I)-diphenylphosphide species was characterized by 31 P NMR spectrum and mass spectrum. At last, three products were transformed to chiral 1,2-bisphosphines, which were employed as ligands in Rh-catalyzed asymmetric hydrogenation of α-amino-α,β-unsaturated ester. The α-amino acid derivative was produced in high enantioselectivity, which demonstrated the utility of the present methodology.

Rapid Synthesis of Chiral 1,2‐Bisphosphine Derivatives through Copper(I)‐Catalyzed Asymmetric Conjugate Hydrophosphination

Abstract1,2‐Bisphosphines have been identified as one class of important and powerful chiral ligands in asymmetric catalysis with transition metals. Herein, a copper(I)‐catalyzed asymmetric hydrophosphination of α,β‐unsaturated phosphine sulfides was developed with the assistance of “soft–soft” interaction between copper(I)‐catalyst and the phosphine sulfide moiety, which afforded 1,2‐bisphosphine derivatives with diversified electronic nature and steric hindrance in high to excellent yields with high to excellent enantioselectivity. Moreover, the challenging catalytic asymmetric hydrophosphination/protonation reaction was achieved with excellent enantioselectivity. Strikingly, the dynamic kinetic resolution of racemic diarylphosphines was also successfully carried out with high to excellent diastereo‐ and enantioselectivities. Interestingly, the nucleophilic copper(I)‐diphenylphosphide species was characterized by 31P NMR spectrum and mass spectrum. At last, three products were transformed to chiral 1,2‐bisphosphines, which were employed as ligands in Rh‐catalyzed asymmetric hydrogenation of α‐amino‐α,β‐unsaturated ester. The α‐amino acid derivative was produced in high enantioselectivity, which demonstrated the utility of the present methodology.

Lone pairs mapping by Laplacian of 3 He NMR chemical shift.

Results of approbation of a new quantum mechanical approach of lone pairs (LPs) visualization, its optimization and testing on a range of model molecules are presented. The main idea of proposed methodology is using 3 He atom as a probe for investigating electronic shells of species with LPs. As model objects, we consider "classical" examples of hydrogen cyanide, methanimine, ammonia, phosphine, formaldehyde, water, and hydrogen sulfide. It is shown that LPs can be visualized by means of 3D maps of Laplacian of 3 He chemical shift ∇2 δHe . NMR calculations could be performed using level of theory as low as B3LYP/6-31G, allowing for the reduction of computational time without significant loss of quality. Advantages of our approach are discussed in comparison with usual methods of lone pairs visualization (electron localization function, molecular electrostatic potential).

Novel phosphine sulphide gold(i) complexes: topoisomerase I inhibitors and antiproliferative agents.

This work describes the synthesis of the gold(i) complexes of phosphine sulphides. The formation of these new derivatives has been confirmed by X-ray crystallography. The coordination of gold(i) with the sulphur atom of the phosphine sulphides favors the inhibition of topoisomerase I as well as a high cytotoxicity of the gold(i)-complexed compounds against the cancer line A549 with IC50 values in the nanomolar range and IC50 values below 5 μM against the SKOV3 cell line. It should be noted that the cytotoxicities observed for the new gold(i) complexes are higher than those observed for phosphine sulphide ligands before binding to gold. Furthermore, the results also indicate that the presence of a nitrogenated heterocycle, such as tetrahydroquinoline or quinoline, is also necessary for the TopI inhibition to be maintained. In addition, no toxicity was observed when the non-cancerous lung fibroblast cell line (MRC5) was treated with the new phosphine sulphide gold(i) complexes prepared.

Oxidative Cross-Coupling of Cysteamine with Secondary Phosphine Chalcogenides: Aspects of Reaction Chemoselectivity

Cysteamine (2-aminoethanethiol) undergoes oxidative cross-coupling with secondary phosphine sulfides and phosphine selenides under mild conditions (room temperature, 2–5 h, CCl4/Et3N) to give products of monocoupling at the amino group (ethylchalcogenophosphinic amides with free SH functions) and dicoupling (l-chalcogenophosphorylamino-2-chalcogenothioethanes) in 72–85% total yield. Under similar conditions, stirring an equimolar mixture of bis(2-phenylethyl)phosphine sulfide (or selenide), 1-butylamine, and 1-butanethiol leads to the chemoselective formation of the corresponding chalcogenophosphinic amides in high yield.

High refractive and low birefringent materials based on Poly(arylene ether phosphine oxide)s and Poly(arylene ether phosphine sulfide)s

Poly(arylene ether phosphine oxide)s and poly(arylene ether phosphine sulfide)s with high refractive indices and low birefringences have been developed. The poly(arylene ether phosphine oxide)s were synthesized by the polycondensation of bis(4-fluorophenyl)phenylphosphine oxide with various bisphenols. Subsequently, the poly(arylene ether phosphine sulfide)s were synthesized by the sulfurization reaction of the poly(arylene ether phosphine oxide)s with Lawesson's reagent. These polymers have excellent thermal stabilities (Td5 > 490 °C), high glass transition temperatures (Tg = 198–281 °C), and no absorption in the visible light region. In addition, they achieve high refractive indices of 1.649–1.675 for the poly(arylene ether phosphine oxide)s and 1.671–1.691 for the poly(arylene ether phosphine sulfide)s owing to the highly polarizable P X (X = O, S) groups in their backbones. Their orientational birefringences (CR values) are in the range from +0.7 × 10−9 to +3.0 × 10−9 Pa−1, which are lower than those of the conventional poly(arylene ether ketone) and poly(arylene ether sulfone) (+7.8 × 10−9 and +4.0 × 10−9 Pa−1, respectively).

Cover Feature: Potent and Selective Cytotoxic and Anti‐inflammatory Gold(III) Compounds Containing Cyclometalated Phosphine Sulfide Ligands (Chem. Eur. J. 62/2019)

Cover Feature: Potent and Selective Cytotoxic and Anti‐inflammatory Gold(III) Compounds Containing Cyclometalated Phosphine Sulfide Ligands (Chem. Eur. J. 62/2019)

Synthesis of α,β-Unsaturated Phosphine Sulfides

α,β-Unsaturated phosphine sulfides may exhibit different reactivity from α,β-unsaturated phosphine oxides toward nucleophilic addition and thus may find new applications in copper(I)-catalyzed asymmetric reactions. Herein, various α,β-unsaturated phosphine sulfides were prepared in moderate to excellent yields from the parent α,β-unsaturated phosphine oxides with Lawesson’s reagent. The reaction enjoys a broad substrate scope and tolerates a variety of functional groups.

Potent and Selective Cytotoxic and Anti-inflammatory Gold(III) Compounds Containing Cyclometalated Phosphine Sulfide Ligands.

Four cycloaurated phosphine sulfide complexes, [Au{κ2 -2-C6 H4 P(S)Ph2 }2 ][AuX2 ] [X=Cl (2), Br (3), I (4)] and [Au{κ2 -2-C6 H4 P(S)Ph2 }2 ]PF6 (5), have been prepared and thoroughly characterized. The compounds were found to be stable under physiological-like conditions and showed excellent cytotoxicity against a broad range of cancer cell lines and remarkable cytotoxicity in 3D tumor spheroids. Mechanistic studies with cervical cancer (HeLa) cells indicated that the cytotoxic effects of the compounds involve the inhibition of thioredoxin reductase and induction of apoptosis through mitochondrial disruption. In vivo experiments in nude mice bearing HeLa xenografts showed that treatment with compounds 4 and 5 resulted in significant inhibition of tumor growth (35.8 and 46.9 %, respectively), better than that of cisplatin (29 %). The newly synthesized gold complexes were also evaluated for their in vitro and in vivo anti-inflammatory activity through the study of lipopolysaccharide (LPS)-activated macrophages and carrageenan-induced hind paw edema in rats, respectively.

Evoking non-bonding S-π interaction by aryl phosphine sulfide for selectively enhanced electronic property of organic semiconductors

Selective tuning of optoelectronic properties of organic semiconductors is one of the most significant challenges in organoelectronics. Herein, on the basis of aryl phosphine sulfide (APS), we show that the electronic performance can be selectively enhanced by evoking the non-bonding S-π interactions between the sulfur atom of APS and π-conjugated carbazole moiety, on account of the large scope 3p lone-pair electrons of S for effective electronic communications. It is indicated that the material properties and device performances are strongly dependent on the beingness of the successfully established intramolecular S-π interaction. Specifically, APS-based DPSSi exhibits excellent solubility and film-forming ability and enhanced carrier transportation and injection abilities at high triplet energy level; and the DPSSi-hosted blue phosphorescent light-emitting diodes (PhOLEDs) show high current efficiency up to 36.6 cd A−1, power efficiency of 30.6 lm W−1, and external quantum efficiency of 20.8%, which are among the best results of blue PhOLEDs reported so far. The semi-conjugation feature of S-π interaction in selectively modulating electronic properties would offer exciting opportunities for settling intrinsic difficulties of organic optoelectronic materials and devices, promoting significantly the development of non-bonding interaction involved organic optoelectronic molecules.

High Triplet Energy Phosphine Sulfide Host Materials with Selectively Modulated Electrical Performance for Blue Electrophosphorescence

Bipolar host materials consisting of electron-donating (D) and -accepting (A) moieties are significant advances in broadening the recombination zone to suppress the quenching effects of emissive ph...

Molecular and crystal structures of tris(3-methylphenyl)phosphine and its chalcogenides

The molecular and crystal structures of tris(3-methylphenyl)phosphine, tris(3-methylphenyl)phosphine oxide, tris(3-methylphenyl)phosphine sulfide and tris(3-methylphenyl)phosphine selenide were determined by X-ray diffraction. It was previously indicated that phosphine oxide should be isostructural with phosphine sulfide and phosphine selenide. However, this statement was not confirmed experimentally: the geometrical structure of the phosphine oxide is closer to the geometry of the phosphine. Tris(3-methylphenyl)phosphine, tris(3-methylphenyl)phosphine sulfide and tris(3-methylphenyl)phosphine selenide crystallize in the orthorhombic space group Pbca, while the phosphine oxide molecules in the crystal are packaged in the space group Pca21 with screw axis.

N,S-containing soft ligands for extractive separation of f-metals: synthesis and unexpected inverse selectivity

A number of heterocycle-based bis(phosphine sulfides) have been synthesized from the corresponding phosphine oxides using phosphorus(v) sulfide in good to excellent yields, for one representative compound the molecular structure has been determined by single crystal X-ray diffraction. The compounds obtained were tested as extractants for f-metals both in nitric acid and ammonium nitrate media, distribution coefficients and selectivity factors have been determined for an Am/Eu pair.