Triphenylphosphine Sulfide Research Articles

Triphenylphosphine Sulfide: a Redetermination at 150K

The structure of triphenylphosphine sulfide, C18H15PS, previously reported (Codding & Kerr, 1978), was undertaken at 150 K in order to discover out new polymorphic forms or phase transitions when lowering the temperature.

31P CP-MAS NMR, Vibrational, and X-Ray Characterization of the Adducts of Triphenylphosphine Sulfide with ICl and IBr

The reactions between triphenylphosphine sulfide (Ph3PS) and ICl in CCl4 and IBr in CH2Cl2 in 1 : 1 molar ratio give the solid adducts Ph3PS · ICl (I) and Ph3PS · IBr (II) whose structures have been solved by X-ray diffraction. Compounds I and II consist of discrete molecule units and feature the S–I–Cl or S–I–Br linear group. The S–I bond distances in I, II (2.641(1), 2.665(1) A respectively) and in compound 2 Ph3PS · 3 I2 (III) (2.729(2) A) are correlable to the net increase in the I–X (X = Cl, Br, I) bond distance. The structural features of I, II and III are in accordance with 31P CP–MAS NMR, FT-Raman and FT-IR spectral data, and elucidate the nature of the donor (Ph3PS)-acceptor (ICl, IBr, I2) interaction. 31P-CP-MAS-NMR, Schwingungs- und Strukturuntersuchung der Addukte von Triphenylphosphinsulfid mit IBr und ICl Die Reaktion zwischen Triphenylphosphin sulfid (Ph3PS) und ICl in CCl4 bzw. IBr in CH2Cl2 im Molverhaltnis von 1 : 1 ergab die festen Addukte Ph3PS · ICl (I) und Ph3PS · IBr (II), deren Strukturen durch Rontgenstrahlenbeugung bestimmt wurden. I und II bestehen aus isolierten Molekuleinheiten mit linearen S–I–Cl- bzw. S–I–Br-Einheiten. Die S–I-Bindungslangen von I und II (2.641(1) bzw. 2.665(1) A) und in 2 Ph3PS · 3 I2 (III) (2.729(2) A) stehen in Beziehung zu den Bindungslangen von I–X (X = Cl, Br, I). Die strukturellen Eigenschaften von I, II und III sind mit den 31P-CP-MAS-NMR-, FT-Raman- und FT-IR-Daten zu deuten und erklaren die Natur der Donor(Ph3PS)-Akzeptor(ICl, IBr, I2)-Wechselwirkung.

Liquid-liquid extraction of mercury(II) with triphenylphosphine sulphide: Application to medicinal and environmental samples

A method is proposed for the separation and determination of mercury(II) in environmental samples after its extraction from salicylate solution using triphenylphosphine sulphide (TPPS) as an extractant. The extraction conditions are optimized and reported. The nature of the extracted species is ascertained by a plot of log of distribution ratio versus log of concentration of salicylate and TPPS.

Radical-chain desulfurisation of α-(alkylthiomethyl)acrylates with triphenylphosphine: a new route to α-alkylacrylates

2-Methylene-3-alkylthiopropanoate esters H 2CC(CO 2Et)CH 2SR react with triphenylphosphine in refluxing octane, in the presence of a peroxide initiator, to give 2-methylenealkanoates H 2CC(CO 2Et)CH 2R in moderate yields, together with triphenylphosphine sulfide.

The chemistry of 5-oxodihydroisoxazoles. Part 22.1 The synthesis of 1,3-oxazin-6-ones from N-thioacylisoxazol-5(2H )-ones

N-Thioacylisoxazol-5(2H)-ones, prepared by the reaction of thiocarbonyl chlorides with isoxazol-5(2H)-ones in the presence of base, are reduced by triphenylphosphine to afford 1,3-oxazin-6-ones and triphenylphosphine sulfide. If the thioacylation is carried out with phenyl chlorodithioformate, the thermal rearrangement of the intermediate, to again form the oxazin-6-one and sulfur, is so rapid that the use of the phosphine is not required. The presence of an ethoxycarbonyl group at C-3, or of a bromine atom at C-4 of the isoxazolone results in the formation of thiazoles.

Crystal structure of triphenylphosphine sulfide diiodine; the first crystallographically characterised 1∶1 molecular charge-transfer complex of a tertiary phosphine sulfide with diiodine

In CH2Cl2 solution, Ph3PS and diiodine react to form a molecular 1∶1 charge-transfer complex. The complex has been studied in solution using 31P-{H} NMR and UV/VIS spectroscopy. Single-crystal X-ray diffraction and solid-state 31P-{H} NMR studies of Ph3PS·I2 show that the molecular structure is maintained in the solid phase. The structure of Ph3PS·I2 is novel and contradicts previous results which indicated that a 1∶1 (Ph3PS∶I2) complex could not be isolated in the solid state. The I–I distance [2.823(1) A] and the S–I distance [2.753(2) A] in Ph3PS·I2 are comparable with those in charge-transfer complexes of related sulfur donors. However, the I–I distance in Ph3PS·I2 is shorter than that in Ph3PSe·I2 reflecting the weaker donor power of the Ph3PS towards diiodine. The NMR spectroscopic results on Ph3PS·I2 and the analogous Ph3PO and Ph3PSe compounds indicate that the stability of the Ph3PE·I2 complexes increases in the order E = Se > S O.

Extraction and separation of silver using triphenylphosphine sulphide.

Silver compounds are used in pharmaceutical and ayurvedic medicines. A method is proposed for the extraction separation of silver from Cu, Cd, Zn, Ni, Pt (IV) and Au (III) from nitrate solution using triphenylphosphine sulphide as an extractant. The recovery of silver is tested both volumetrically and/or by ICP-AES technique.

Enthalpy of formation of triphenylphosphine sulfide

The first measurements of the enthalpies of combustion, sublimation, and fusion of an organo-phosphorus sulfide, triphenylphosphine sulfide, are reported: δcH m o (C18H15PS, cr)=−(10752.58 ±2.90), δsubH m o (C18H15PS, 403 K)=(136.80±6.09), and δfusH m o (C18H15PS, Tm=435.92 K) =(30.53±0.21) kJ·mol−1. Correction of the phase change enthalpies toT=298.15K and po =0.1 MPa results in the standard phase change enthalpy values of δsubH m o (298.15 K)=(142.8 ±6.8) and δfusH m o (298.15 K)=(19.28±0.21) kj·mol−1. Accordingly, the enthalpies of formation of solid, liquid, and gaseous triphenylphosphine sulfide are derived: δfH m o (C18H15PS, cr) =(63.20±2.56), δfH m o (C18H15PS, l)=(82.48±2.57), and δfH m o (C18H15PS, g)=(206.0±7.3) kJ·mol−1. From these ancillary data, the P=S double-bond enthalpy is 394 kJ-mol−1 and in good agreement with earlier reaction calorimetry results. These phosphorus sulfide values are compared with those for the arsenic sulfides. Plausibility arguments are given for our results.

SCN − effect on the palladium(II) transfer in two and three phases systems using triphenylphosphine sulfide as a carrier

The extraction of Pd(II) by triphenylphosphine sulfide (TPPS) in toluene from hydrochloric acid solutions containing small amounts of SCN − has been investigated. The role of thiocyanate on the Pd(II) extraction is explained as a trans-effect with the formation of mixed complexes PdC l4− n (SCN) n 2−, less inert to ligand substitution than the chloride complexes. The analysis of metal distribution data by numerical calculations suggested the formation of the species Pd(SCN) 2·TPPS and Pd(SCN) 2·2TPPS in the organic phase with formation constants log K 021 = 13.00 and log K 022 = 14.24, respectively. A comparison of the results with those obtained using triisobutylphosphine sulfide (TIBPS) under similar conditions reveals a lower influence of SCN − concentration and also lower values for Pd(II) extraction, which can be attributed to the electron withdrawing characteristics of the aromatic ring with a decrease of the solvating power of the S atom for TPPS. The results obtained on Pd(II) distribution have been exploited in a three phases system by implementing a solid supported liquid membrane, being thiocyanate concentration the driving force of the mass transfer process. The behavior of the system is similar to that observed in the two phases.

DETERMINATION OF THE31P NMR CHEMICAL SHIELDING TENSOR ANISOTROPY OF SOME MOLECULES IN SOLUTION

Abstract The chemical shielding tensor anisotropy of the 31P nucleus in tris(piperidino)phosphine oxide and triphenylphosphine sulfide molecules was determined in solution from 31P and 13C spin-lattice relaxation time measurements. The quadrupolar coupling constant χ of the 17O nucleus of tris(piperidino)phosphine oxide was also deduced from these experiments and 17O NMR spectra. The δ[sgrave] value for triphenylphosphine sulfide is compared to those reported in the literature. The δ[sgrave] and χ parameters for tris(piperidino)phosphine oxide are discussed in terms of the influence of the piperidino substituent on the electronic distribution in the PO bond.

Crystal structure and low-temperature emission of 2,9-dimethyl-1, 10-phenanthrolinebis(triphenylphosphinesulfide)copper(I)

The synthesis and crystal structure of a luminescent Cu(I) complex containing triphenylphosphine sulfide and the α-diimine 2,9-dimethyl-1, 10-phenanthroline (dmp) is described. The coordination geometry about the Cu(I) center is pseudo-tetrahedral. Interplanar interactions between phenyl groups on the phosphine sulfide ligands and the phenanthroline exist, but are significantly less than those previously reported for the Cu(I) triphenylphosphine analog. The complex displays emission from a single metal-centered charge-transfer state at 77K in a 4∶1 ethanol/methanol (v/v) glass. This is in contrast to the triphenylphosphine complex, which exhibits dual luminescence from a charge-transfer and an intraligand state at 77K. Crystal data: orthorhombic, P212121,a=9.4226(9) A,b=15.757(1) A,c=30.494(6) A,V=4527.4(6) A3, andR=0.053 (1021 reflections).

Tris(2,6-dimethoxyphenyl)phosphine sulfide monohydrate

The title compound C 24 H 27 O 6 PS.H 2 O, or Φ 3 PS.H 2 O [Φ=2,6-(CH 3 O) 2 C 6 H 3 ], has an average P-C bond length of 1.840 A, a P=S length of 1.971 (2) A and an average C-P-C angle of 107.1 o , which are considerably longer and wider than those of triphenylphosphine sulfide, with values of 1.817, 1.950 A and 105.7 o , respectively. Intramolecular distances between the six methoxy O atoms and the P atom are all shorter than the sum of van der Waals radii of O and P atoms, implying the presence of direct electron donation from the methoxy O atoms to the P atom

Palladium extraction by triphenylphosphine sulfide in benzene

The extraction of Pd(II) by triphenylphosphine sulfide (Ph3PS) in benzene from nitric acid solutions has been investigated. The effect of different parameters on the extraction of palladium was studied. Based on the results, an equilibrium model is proposed. The stoichiometry of the extracted species was elucidated and found to be Pd(NO3)22Ph3PS. Possible interference with selected radionuclides that might exist in high level liquid waste was investigated and discussed.

Organophosphorus compounds as coke inhibitors during naphtha pyrolysis. Effect of benzyl diethyl phosphite and triphenylphosphine sulfide

This paper reports that significant reduction in the rate of coke formation during naphtha pyrolysis was achieved by adding benzyl diethyl phosphite or triphenylphosphine sulfide to the feed. Although the yield of carbon oxides was reduced, there was no effect of these additives on the hydrocarbon yields. Addition of these organophosphorus compounds significantly reduced the concentration of metals, such as iron, nickel, and chromium, incorporated in the coke. A previously proposed model for coke inhibition due to the formation of a passivating metal-phosphorus complex could satisfactorily correlate the data.

Acetone-induced triboluminescence of triphenylphosphine

The triboluminescence of triphenylphosphine has been found to be acetone-dependent and is positively correlated with acetone content, crystal size, and negatively correlated with the age of the crystal. There is no measurable difference in the unit cell dimensions of triboluminescent triphenylphosphine crystallized from acetone and those of inactive material from cyclohexane. Similar emission results are obtained from crystals obtained from saturated solutions in some, but not all carbonyl-containing solvents, and from methanol and ethanol but not diethyl ether or ethyl acetate. Inactive material was also obtained from saturated solutions in benzene, cyclohexane or chloroform. The triboluminescence and photoluminescence maxima and bandwidths were the same, within the error limits of the experimental method and instrumentation used, for triphenylphosphine crystallized from acetone, acetonitrile, or cyclohexanone. Among the other highly arylated hetero-organics tested in measures to extend this correlation, triphenylamine and 1,2,5-triphenylphosphole were triboluminescent as purchased or prepared and when recrystallized from acetone, cyclohexane and several other solvents. Tritylamine, triphenylphosphine oxide, and triphenylphosphine sulfide were not triboluminescent as purchased or prepared, or when re-crystallized from acetone or cyclohexane.

Reactivity of molybdenum and tungsten disilene complexes

The reactions of the η 2 -disilene complexes Cp 2M(η 2-Me 2SiSiMe 2) (M = Mo, 1a; W, 1b) with a variety of inorganic and organic substrates are reported. Compound 1a reacts with methanol to yield Cp 2Mo(SiMe 2H)(SiMe 2OMe) ( 2,> 80%) and Cp 2Mo(H)(Si Me 2SiMe 2OMe) ( 3, < 20%), products of SiSi and MoSi bond cleavages. Nucleophilic attack by methylenetrimethylphosphorane leads to opening of the MoSi 2 ring and yields the disilyl-substituted ylide Cp 2Mo(H)(SiMe 2SiMe 2CHPMe 3) ( 4). Although oxygen atom sources such as O 2, N 2O, epoxides and Ph 3PO do not react cleanly with 1, reaction with elemental sulphur yields the symmetrical sulphur-atom insertion product cyclo-Cp 2MO (SiMe 2SSiMe 2) ( 5). In contrast, reaction with triphenylphosphine sulphide principally yields the unsymmetrical insertion product cyclo-Cp 2Mo(SiMe 2SiMe 2S) ( 6). Compounds 5 and 6 have been characterized by X-ray diffraction studies. Insertion into the SiSi bond of 1a and 1b is also observed in reactions with trimethylsilylazide and carbon dioxide, which yield cyclo-Cp 2Mo(SiMe 2N(TMS)SiMe 2) ( 7) and cyclo-Cp 2W(SiMe 2C(O)OSiMe 2) ( 10), respectively. Benzophenone also appears to insert between the two silicon atoms in 1a to yield a five-membered ring compound, but the instability of this product has precluded a definitive assignment of the structure. The four-membered ring compound cylo-Cp 2Mo (SiMe 2) 3 ( 8) has been identified in the reaction of 1a with dimethylsilylene, generated by the thermolysis of hexamethylsilacyclopropane. Dimethylsilylene insertion is relatively unselective in non-coordinating solvents such as benzene, and the secondary insertion product cyclo-Cp 2Mo(SiMe 2) 4 ( 9) is also produced. However, only 8 is formed in tetrahydrofuran, an observation which can be attributed to the higher selectivity of the intermediate silylene-base adduct formed in the coordinating solvent.

Structure and reactivity of a titanocene (.eta.2-thioformaldehyde) trimethylphosphine complex

Bis(η 5 -cyclopentadienyl) titanium titanocene η 2 -thioformaldehyde trimethylphosphine (3) was prepared from titanocene methylidene trimethylphosphine and either sulfur-containing compounds (e.g., alkene sulfides, triphenylphosphine sulfide) or elemental sulfur. The complex 3 reacted with methyl iodide to produce the cationic titanocene η 2 -thiomethoxymethyl trimethylphosphine complex 5a.

Solvent Extraction of p-Nitrophenol into Cyclohexane with Phosphines and Their Derivatives

The solvent extraction of p-nitrophenol from aqueous acid solutions into cyclohexane with trioctylphosphine (TOP), trioctylphosphine oxide (TOPO), triphenylphosphine (TPP), triphenylphosphine oxide (TPPO) and triphenylphos-phine sulfide (TPPS) was examined. The results were compared with those with trioctylamine (TOA). The extracted p-nitrophenol was found to form a 1:1 hydrogen-bonded associate with bases in the organic phase. The association constant in the organic phase was greater in the order TOPO>TPPO>TOP>TOA>TPPS>TPP. The ability of an extractant for an acid is considered from its chemical properties as a base in the organic phase. It was concluded that it may be related to the association constant with the acid in the solvent.

ChemInform Abstract: Some Copper(I) Perthiocarboxylates and Their Reactions with Tertiary Phosphines. Crystal Structure of Tetra(p‐tolyldithiocarboxylato)tetracopper(I), (CuS2C‐p‐tolyl)4, and of (Bis(triphenylphosphine)(p‐tolyldithiocarboxylato)copper(I)) Triphenylphosphine Sulfide, (CuS2C‐p‐tolyl(PPh3)2)·PPh3S.

AbstractThe Cu(I) perthiocarboxylates (I) are prepared in high yields by known methods from corresponding aldehydes and ammonium polysulfides in basic medium.

On some copper(I) perthiocarboxylates and their reactions with tertiary phosphines. Crystal structure of tetra( p-tolyldithiocarboxylato)tetracopper(I), [CuS 2C- p-tolyl] 4, and of [bis(triphenylphosphine)( p-tolyldithiocarboxylato)copper(I)] triphenylphosphine sulfide, [CuS 2C- p-tolyl(PPh 3) 2]·PPh 3S

Some copper(I)perthiocarboxylates [CuS 3CAr] 4 ( I) ( Ia, ArPh; Ib, Ar p-tolyl) were prepared in high yields from the corresponding aldehydes and ammonium polysulfide in basic medium. By reacting them with triphenylphosphine in different ratios, formation of PPh 3S occurred and the following series of products could be isolated: [(CuS 3CAr) 2(CuS 2- CAr) 2]py 2 ( II); [CuS 2CAr] 4 ( III); [(CuS 2CAr) 4- (PPh 3) 2] ( IV); [CuS 2CAr(PPh 3) 2] ( V). In the case of p-tolyl the complex [CuS 2CAr(PPh 3) 2]·PPh 3S ( VIb) was also obtained. Some significant IR and NMR ( 13C, 31P) data of the above compounds are reported. The crystal structures of compounds IIIb and VIb were established by single crystal X-ray diffraction methods. Crystals of IIIb are triclinic, space group P 1 , with a=13.879(4), b=10.324(3), c=13.479(4) Å,α=99.04(2), β=113.31(3), γ= 92.34(2)° and Z=2. Crystals of VIb are also triclinic, space group P 1 , with a=15.833(5), b= 10.999(3), c=15.690(5) Å, α=103.12(3), β= 90.88(2), γ=94.05(2)° and Z=2. The structures have been solved by direct and Fourier ( IIIb) and by Patterson and Fourier ( VIb) methods and refined by blocked full-matrix least-squares to R=0.059 for IIIb and R=0.051 for VIb. The structure of IIIb consists of discrete units of four copper atoms bound to sulfur atoms from four p-tolyldithiocarboxylate groups acting as tridentate ligands. A sulfur atom of each ligand coordinates to one only copper atom and the other bridges two adjacent metals so that each metal is pseudo-trigonally surrounded by three sulfur atoms. In the structure of VIb monomeric complexes are present in which the metal atom is pseudo-tetrahedrally coordinated by two phosphorous atoms from triphenylphosphine ligands and by two sulfur atoms from one chelating p-tolyldithiocarboxylate group. Triphenylphosphine sulfide molecules are also present in the crystals of VIb. The complex autoxidative reactions of some dithiocarboxylates in pyridine, which cause a partial transformation of the sulfur atoms in coordinated ‘SO 4’ groups, were also investigated.