Triphenylphosphine Selenide Research Articles

Application of triphenylphosphine organic compounds constructed with O, S, and Se in aluminum ion batteries

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 AlCl2+. The molecular structure of triphenylphosphine and its combination with Se offers an enticing pathway for designing cathode materials in aluminum-organic batteries.

Phosphinine Selenide: Noncovalent Interactions with Organoiodines and Elemental Iodine, and Reactivity towards Potassium Cyanide.

A co-crystalline adduct consisting of a phosphinine selenide and an organohalide was obtained by slow evaporation of the solvent from a mixture of 2,6-bis(trimethylsilyl)phosphinine selenide and 1,4-diiodotetrafluorobenzene (1,4-TFDIB). The crystallographic characterization of the product shows π-π stacking, F⋅⋅⋅H hydrogen bonding between 1,4-TFDIB and the phosphinine selenide, as well as F⋅⋅⋅F interactions between 1,4-TFDIB molecules. Moreover, the phosphorus heterocycle could be crystallized with diiodine to form a 1 : 1 adduct. The d(I-I) distance in this compound is 2.8475(3) Å, which is shorter than the corresponding one in triphenylphosphine selenide diiodide, reflecting the weaker net-donor power of the phosphinine selenide towards diiodine. The phosphinine selenide could also be used as a selenium transfer reagent to generate KSeCN from KCN.

Anion chemistry enabled positive valence conversion to achieve a record high-voltage organic cathode for zinc batteries

<h2>Summary</h2> Chalcogens undergoing positive valence conversions show great potential to achieve a high discharge voltage in batteries; however, such reactions with high reversibility are difficult to achieve because element O/S/Se are inherently electron acceptors. Herein, by incorporating the chalcogens with the unique triphenylphosphine-based structure (strong electron-withdrawing groups), a high-potential triphenylphosphine selenide organic cathode (TP-Se) is developed. Facilitated by a Zn²⁺/trifluoromethanesulfonate (OTF⁻) hosting mechanism, the (TP-Se)⁻ to (TP-Se)⁰ to (TP-Se)⁺ conversion is realized. The dual-ion Zn‖TP-Se batteries exhibit a flat discharge plateau at 1.96 V and a superior discharge capacity. Benefiting from the stable triphenylphosphine molecular structures and optimized hybrid electrolytes, excellent cycling performance is also attained (up to 85.3% capacity retention after 4,300 cycles). Moreover, the Zn‖TP-Se battery also delivers a remarkable rate performance. The system is attractive due to its high discharge voltage, which is higher than ever reported for organic cathodes of zinc batteries.

Brønsted Acid‐Catalyzed Enantioselective Iodocycloetherification Enabled by Triphenylphosphine Selenide Cocatalysis

AbstractEnantioselective iodocycloetherifications can be conducted using sterically highly demanding BINOL‐based phosphoric acid diesters as catalyst. To achieve highly enantioselective reactions, cocatalysis by triphenylphosphine selenide is necessary. With cocatalysis, good to excellent enantioselectivities can be achieved for a broad range of substrates using catalyst and cocatalyst loadings as low as 1 mol %. The triphenylphosphine selenide cocatalyst itself does not strongly influence diastereoselectivity, but leads to higher reactivity and, in combination with a BINOL‐based phosphoric acid diester, to good enantioselectivity.magnified image

Lewis Base/Brønsted Acid Cocatalysis for Thiocyanation of Amides and Thioamides.

Lewis base/Brønsted acid cocatalysis for electrophilic thiocyanation of olefins is reported. Using a combination of triphenylphosphine selenide and diphenyl phosphate as a catalyst, a wide range of unsaturated amides and thioamides underwent thiocyanation to furnish thiocyanated thiazoline and oxazoline derivatives in high yields (up to 97%).

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.

Benzylic bromination catalyzed by triphenylphosphine selenide via Lewis basic activation

The synthesis of benzyl bromides was achieved under mild reaction conditions using N-bromosuccinimide as a bromine source and triphenylphosphine selenide as a catalyst. These conditions were compatible with a variety of substrates including boronic esters, protected amines to give imines, and carboxylic acids (to give phthalides when ortho to the benzylic center). A preliminary mechanistic investigation utilizing calculated bond dissociation energies (BDE) is employed to rationalize how a Lewis base can activate a radical mechanism.

Organometallic synthesis, structure determination, shape evolution, and formation mechanism of hexapod-like ternary PbSe(x)S(1-x) nanostructures with tunable compositions.

The fabrication of hexapod-like ternary PbSexS1-x nanostructures has been reported via an alternative organometallic route from reaction of Pb(II) salt with triphenylphosphine selenide (Ph3PSe) and dibenzyl disulfide (DBDS) in dibenzylamine (DBA) with addition of oleic acid (OA) at 260 °C. The shape, structure, and composition of the nanostructured hexapods are investigated and determined by techniques of XRD, SEM, TEM, Raman, HRTEM, SAED, XPS, EDX, and HAADF-STEM, and the obtained ternary nanostructured hexapods are of typical rock salt phase with Pb-rich features without phase separation, and their compositions could be systematically regulated by facile variations of reaction parameters. Investigations reveal that the successful fabrication of the ternary hexapods with tunable compositions is resulted from the effective selection of Se and S sources of Ph3PSe and DBDS that have similar reactivity in the current reaction system along with small lattice mismatch between the two end members of PbSe and PbS. Generally, the relations between the composition and lattice parameters for the ternary nanostructures obtained in DBA with varied addition of OA exhibit linear slops that are consistent well with Vegard's law. Interestingly, intensive investigations show that the nanostructures are mainly gradiently alloyed nanostructures with somewhat chalcogen-element segregations or disorders rather than homogeneously alloyed solid-state solutions due to kinetic limitation for short reaction time even though thermodynamics is feasible in the system, and also, high concentration of S element in the feedstocks tends to relative high density of disorders in the ternary nanostructures. Based on the revealing of the formation mechanism for the nanostructures with varied microstructures, the ternary PbSexS1-x hexapods can be tuned from gradient alloys with segregations to approximately homogeneous via enlongating reaction time. In addition, the photolysis of the nanostructures to lead oxysulfate and oxyselenate species is evidenced at ambient condition via Raman detection although they are stable at -190 °C.

Organometallic-Route Synthesis, Controllable Growth, Mechanism Investigation, and Surface Feature of PbSe Nanostructures with Tunable Shapes

Lead selenide (PbSe) nanostructures with well-defined star-shaped morphology are successfully fabricated via a facile organometallic synthetic route from the reaction of tetraphenyl lead (Ph4Pb) with triphenylphosphine selenide (Ph3PSe) in dibenzylamine (DBA) with the assistance of oleic acid (OA) and oleylamine (OAm) at 220 °C for 30 min. The structure and shape of the nanocrystals are investigated by techniques of XRD, SEM, TEM, HRTEM, SAED, and EDX, and it is interesting that the obtained PbSe nanostars present Pb-rich features, although the PbSe nanostars are still in typical rock salt phase. Experimental investigations and ATR-FTIR studies demonstrate that the media of DBA, OA, and OAm with an order OA > DAB > OAm play important roles in the growth of the PbSe nanostars with well-defined shapes because the media not only serve as solvents but capping materials. The synergetic effects of the media are also favorable for the growth of PbSe nanocrystals with the well-defined star-shaped morphologies in the current reaction system. Meanwhile, varied PbSe nanostructures with cubic, side-cut cubic, and octahedral shapes can be fabricated by regulating the relevant reaction conditions, and all of these nanostructures prepared in the procedures demonstrate Pb-rich features due to the selective capping effects of the media to the exposed Pb(II) ions. It is confirmed that the specific shape and geometry of the nanostructures can be tuned by controlling the exposed crystal surfaces and/or the corresponding compositions via the variation of reaction conditions in the media.

Complementary Selenium···Iodine Halogen Bonding and Phenyl Embraces: Cocrystals of Triphenylphosphine Selenide with Organoiodides

Se···I Halogen bonding (XB) between triphenylphosphine selenide and organoiodides: 1,2-diiodotetrafluorobenzene (1,2-F4DIB), 1,4-diiodotetrafluorobenzene (1,4-F4DIB), and tetraiodoethylene (TIE) has been used to assemble molecules into finite adducts, chains, and two-dimensional layers. Phenyl embraces involving the triphenylphosphine groups extend these moieties into additional dimensions, leading in two cases (1,4-F4DIB and TIE) to open structures, with filled or partially filled cavities. Comparison of structural parameters for 26 reported zigzag chains of embracing Ph3XY reveals that this synthon can adapt its registry to accommodate widely diverse structures. The strengths of the XB interactions were analyzed using natural bond orbital (NBO) theory, which provides an estimate of the energy of a donor–acceptor interaction (ΔEd→a) through localization of the molecular orbitals. Structures of 1:1 and 1:2 XB complexes of Ph3P═Se with 1,2-F4DIB and 1,4-F4DIB were optimized at the DFT(B97-1)/BSI level. The bond distance and angles obtained are in reasonably good agreement with the experimentally observed structures.

Cycloaurated triphenylphosphine-sulfide and -selenide

The first examples of cycloaurated phosphine sulfides and triphenylphosphine selenide have been synthesised; these complexes are fairly rare examples of gold(iii) complexes with potentially reducing sulfur- and selenium-donor ligands. The cycloaurated complex (AuCl(2)(2-C(6)H(4)P(S)Ph(2)) was synthesised in good yield by transmetallation of the organomercury precursor Hg(2-C(6)H(4)P(S)Ph(2))(2) with Me(4)N[AuCl(4)]. A route to the chloro-mercury analogue ClHg(2-C(6)H(4)P(S)Ph(2)) was developed by reaction of the cyclomanganated triphenylphosphine sulfide (CO)(4)Mn(2-C(6)H(4)P(S)Ph(2)) with HgCl(2); this mercury substrate was also used in the synthesis of AuCl(2)(2-C(6)H(4)P(S)Ph(2)). The cycloaurated triphenylphosphine selenide complex AuCl(2)(2-C(6)H(4)P(Se)Ph(2)) was synthesised by an analogous methodology using the new phosphine selenide Hg(2-C(6)H(4)P(Se)Ph(2))(2) [prepared from Hg(2-C(6)H(4)PPh(2))(2) and elemental Se under sonication]. The phosphonamidic analogue AuCl(2)(2-C(6)H(4)P(S)(NEt(2))(2)) has also been synthesised from PhP(S)(NEt(2))(2)via lithiation and mercuration. X-Ray crystal structures of several compounds are reported, and show the presence of puckered ring systems.

Crystal structures of the selenium- and bromo-bridged copper(I) dimers [Cu2(μ2-Br)2(SePPh3)2 · (NCCH3)2] and [Cu2I2(μ3-dppm-Se,Se)2] · 2CH3CN

Reactions of copper(I) halides with Se-donor ligands, namely, triphenylphosphine selenide (Ph3PSe) and bis(diphenylselenophosphinyl)methane (dppm-Se,Se) yielded bromo-bridged [Cu2(μ2-Br)2(SePPh3)2(NCCH3)2] (1), and selenium-bridged, [Cu2I2(μ3-dppm-Se,Se)2] · 2CH3CN (2) dimers, whose crystal structures are described. Acetonitrile stabilizes 1 by coordinating and helps to stabilize the packing in crystals of 2.

Silver(I) complexes of imidazolidine-2-thione and triphenylphosphines: Solid-state, solution NMR and antimicrobial activity studies

Mixed ligand complexes of Ag(I) with triphenylphosphine (PPh3), triphenylphosphine sulfide (SPPh3), triphenylphosphine selenide (SePPh3) and Imidazolidine-2-thione (Imt) have been prepared. The solution as well as solid state NMR studies have been carried out to characterize these complexes. Both solid and solution NMR show the coordination via thione group on one side and (S/Se) or PPh3on the other side. A higher antimicrobial activity is shown by [ImtAgPPh3]Cl complex against gram negativePseudomonas aeruginosa(P. aeruginosa) andEscherichia coli(E. coli) compared to the other two complexes i.e. [ImtAgSPPh3]Cl and [ImtAgSePPh3]Cl.

C–H bond activation through steric crowding of normally inert ligands in the sterically crowded gadolinium and yttrium (C 5 Me 5 ) 3 M complexes

Synthesis of the sterically crowded Tris(pentamethylcyclopentadienyl) lanthanide complexes, (C5Me5)3Ln, has demonstrated that organometallic complexes with unconventionally long metal ligand bond lengths can be isolated that provide options to develop new types of ligand reactivity based on steric crowding. Previously, the (C5Me5)3M complexes were known only with the larger lanthanides, La-Sm. The synthesis of even more crowded complexes of the smaller metals Gd and Y is reported here. These complexes allow an evaluation of the size/reactivity correlations previously limited to the larger metals and demonstrate a previously undescribed type of C5Me5-based reaction, namely C-H bond activation. (C5Me5)3Gd, was prepared from GdCl3 through (C5Me5)2GdCl2K(THF)2, (C5Me5)2Gd(C3H5), and [(C5Me5)2Gd][BPh4] and structurally characterized by x-ray crystallography. Although Gd3+ is redox-inactive, (C5Me5)3Gd functions as a reducing agent in reactions with 1,3,5,7-cyclooctatetraene (COT) and triphenylphosphine selenide to make (C5Me5)Gd(C8H8), [(C5Me5)2Gd]2Se2, and [(C5Me5)2Gd]2Se depending on the stoichiometry used. When the analogous synthetic method was attempted with yttrium in arene solvents, the previously characterized (C5Me5)2YR complexes (R=C6H5, CH2C6H5) were isolated instead, i.e., C-H bond activation of solvent occurred. To avoid this problem, (C5Me5)3Y was synthesized in high yield from [(C5Me5)2YH]2 and tetramethylfulvene in aliphatic solvents. Isolated (C5Me5)3Y was found to metalate benzene and toluene with concomitant formation of C5Me5H, a reaction contrary to the normal pKa values of these hydrocarbons. In this case, the normally inert (C5Me5)1- ligand engages in C-H bond activation due to the extreme steric crowding.

Preparation of Nucleoside H-Phosphonoselenoate Monoesters Via the Phosphinate Approach

An efficient entry to nucleoside 3′-H-phosphonoselenoate monoesters via phosphinate intermediates was developed. It involves a reaction of suitably protected nucleosides with triethylammonium phosphinate in the presence of pivaloyl chloride, followed by selenization of the intermediate nucleoside phosphinates with triphenylphosphine selenide, to produce the corresponding nucleoside H-phosphonoselenoates in 86–92% yields.

Polynuclear selenido–carbonyl manganese complexes derived from tertiary phosphine selenides

The reactions of some phosphine selenides with mononuclear and dinuclear manganese complexes have been investigated. The reactions of Cp′Mn(CO) 2(THF) ( 1) with bis(diphenylphosphino)ethane diselenide (dppeSe 2) affords [(Cp′Mn) 2(μ-Se) 2(CO) 2(dppe)] ( 4), identified by spectroscopic techniques. Complex CpMn(CO) 2(THF) ( 2), by reacting with bis(diphenylphsphino)methane monoselenide (dppmSe) gives a variety of products, [(CpMn) 2(μ-Se) 2(CO) 3(dppm)] ( 5), [CpMn(CO) 2(dppm)] ( 6), [(CpMn) 2(CO) 4(μ-dppm)] ( 7), [CpMn(CO) 2(dppmSe)] ( 8) have been identified (Cp=η 5-C 5H 5, Cp′=η 5-C 5H 4Me, THF=tetrahydrofuran). Finally the reactions of [Mn 2(CO) 8(MeCN) 2] ( 3) with diphenylmethylphosphine selenide (dpmpSe) and triphenylphosphine selenide (tppSe) afford clusters with molecular formula [Mn 4(μ 3-Se) 2(μ-CO)(CO) 14(dpmp) 2] ( 9) and [Mn 4(μ 3-Se) 2(μ-CO)(CO) 14(tpp) 2] ( 10), respectively. The structure of 9 has been determined by X-ray diffraction methods.

Novel formation of 1,2,4-triselenolanes by the reaction of tert-butylarylmethylenetriphenylphosphoranes with elemental selenium

Reaction of tert-butylarylmethylenetriphenylphosphoranes with elemental selenium afforded the corresponding 1,2,4-triselenolanes ( 1 ), 1,3-diselenetanes ( 4 ), and triphenylphosphine selenide. Triselenolanes 1 were formed from selenation of 4 , which may suggest a stepwise selenation of selenoketones.

Structural confirmation of 15-norlubiminol and 15-norepilubiminol, isolated from Solanum aethiopicum, by chemical conversion from lubimin and epilubimin, and their antifungal activity.

15-Norlubiminol and 15-norepilubiminol were obtained from Solanum aethiopicum as an inseparable 1:1 mixture in a relatively poor yield to that of the major phytoalexins, lubimin and epilubimin. Their structures were confirmed by chemical conversion starting from lubimin and epilubimin. Baeyer-Villiger oxidation of the protected lubimins with m-chloroperoxybenzoic acid provided the desired formates. Deoxygenation with triphenylphosphine selenide and subsequent methanolysis provided 15-norlubiminols, whose 1H-NMR spectra were respectively identical with that of the corresponding isomer in the natural 15-norlubiminol mixture. The antifungal activity of 15-norlubiminols would be weaker than that of lubimins.

A new selenium-transferring reagent—triphenylphosphine selenide

Triphenylphosphine selenide and its polymer-supported counterpart are found to be efficient selenium-transferring reagents for the conversion of H-phosphonate diesters and phosphite triesters into the corresponding phosphoroselenoate derivatives.

The reaction of triphenylphosphine selenide with triosmium clusters: a facile cluster coupling through a selenium atom

The room temperature reactions of Ph3PSe with the triosmium clusters Os3(CO)11(CH3CN), Os3(CO)10(CH3CN)2 and Os3(μ-H)2(CO)10 have been investigated. The reaction with an equimolar amount of Os3(CO)11(CH3CN) afforded the known clusters Os3(μ3-Se)2(CO)9, 1, and Os3(CO)11(PPh3), 2, and the new cluster Os3(μ3-Se)(CO)9(PPh3), 3. The analogous reaction with Os3(CO)10(CH3CN)2 gave 1 and 2; reaction with 0.5 equivalent of the cluster gave 1 quantitatively. The reaction with Os3(μ-H)2(CO)10 gave two new clusters, viz. Os3(μ3-Se)(μ-H)2(CO)8(PPh3), 4a, and Os6(μ3-Se)(H)(μ-H)3(CO)18(PPh3)2, 5a. Single crystal structures of 3, 4a and 5a have been obtained. Cluster 3 possesses bridging carbonyls; these appear to have been lost on elongation of the osmium–osmium bonds by bridging hydrides in 4a. The structure of 5a is novel and comprises a naked μ3-Se atom bridging two triosmium moieties; an Os3(μ-H)(CO)10 unit and an Os3(H)(μ-H)2(CO)8(PPh3)2 unit.