Reaction of Sulfur with Ga-C Bonds: Synthesis and Characterization of [PyRGaS](3) Formed from Ga(S(2)R)(3) (R = Et, Me)

The reactions of Ga(CH(2)CH(3))(3) with variable amounts of elemental sulfur, S(8), in toluene or benzene at different temperatures result in the insertion of sulfur into the Ga-C bonds to form the compounds Ga[(S-S)CH(2)CH(3)](3) (I) and Ga[(S-S-S)CH(2)CH(3)](3) (II). Compound I was isolated from the reaction at low temperature while at room temperature; compound II was the major product. Compound II exhibited the maximum extent of sulfur insertion even when the reactions were carried out with more than 9.0 equiv of sulfur. The reactions of Ga(CH(3))(3) with various amounts of sulfur in toluene or benzene only result in the formation of compound III, Ga[(S-S)CH(3)](3). In pyridine at -30 degrees C, deinsertion of the sulfur atoms from Ga-S-S-C bonds was observed for the first time from compounds I and III resulting in formation of the six-membered Ga-S ring compounds IV, [PyEtGaS](3), and V, [PyMeGaS](3), respectively. Compounds IV and V were characterized by (1)H NMR, (13)C NMR, elemental analyses, thermogravimetric analysis, and single-crystal X-ray diffraction. Compound IV crystallized in the monoclinic space group P2(1)/n, with a = 9.288(2) ?, b = 14.966(2) ?, c = 19.588(3) ?, beta = 90.690(10) degrees, and Z = 4. Compound V crystallized in the monoclinic space group P2(1)/c, with a = 10.385(1) ?, b = 15.300(2) ?, c = 15.949(2) ?, beta = 107.01(1) degrees, Z = 4, unit cell volume = 2423.5(5) ?(3), R = 0.030, and R(w) = 0.026. The sulfur insertion reaction pathway was investigated by time-dependent and variable-temperature (1)H NMR spectroscopy.     

O-(1-芳硫基-3-铵基)异丙基-O-2-(N3-替加氟)乙基硫代磷酯的合成及其抗癌活性

六乙基亚磷酰三胺与羟乙基替加氟、1-芳硫基甘油及硫一锅反应得到环甘油硫代磷脂替加氟缀合物(2),三乙胺对2进行亲核开环合成了O-(1-芳硫基-3-铵基)异丙基-O-2-(N3-替加氟)乙基硫代磷酯(3)。2和3的结构经1HNMR,31PNMR和元素分析表征。生物活性测试结果表明,3对膀胱癌细胞PGA1有一定的抑制作用。     

Convenient method for the synthesis of 5-(4-methoxyphenyl)-3H-1,2-dithiole-3-thione (ADT-OMe) and 5-(4-hydroxyphenyl)-3H-1,2-dithiol-3-thione (ADT-OH) using microwave irradiation

A convenient method is described for the rapid synthesis of 5-(4-methoxyphenyl)-3H-1,2-dithiole-3-thione (ADT-OMe) from anethole and elemental sulfur using microwave irradiation. Various reaction conditions were applied to reduce the reaction time from several hours to 10 min, resulting in an improvement in yield and overcoming the undesired by-product formation associated with conventional methods. 5-(4-Hydroxyphenyl)-3H-1,2-dithiol-3-thione (ADT-OH) was obtained by the deprotection of ADT-OMe using pyridine hydrochloride under microwave irradiation.     

Influence of elemental sulfur and mercaptans on corrosion of copper strips in the ASTM D-130 test by means of electronic microscopy (SEM) and energy dispersive X-ray (EDX)

Summary Crude petroleum contains sulfur compounds, most of which are removed during refining. The corrosivity of sulfur compounds present in petroleum products is measured by means of the ASTM D-130 copper strip test, which is based on discoloration of a standard copper strip immersed into the petroleum products at 50°C for 3 h. Here the corrosivity of copper strips are tested with elemental sulfur and different mercaptans in synthetic naphtha. The great corrosive power of elemental sulfur is 3.7 times higher than that of ethylmercaptan, the most corrosive among the different mercaptans. The elemental sulfur and ethyl-mercaptan corrosion distribution on copper strips is also studied by means of the ASTM D-130 test together with electronic microscopy (SEM) and energy dispersive X-ray (EDX) techniques. These non-destructive techniques allow to know the strip corrosive morphology and to determine the sulfur concentration on the strip.     

Reaction of sulfur with poly(vinyl chloride)

The reaction of elemental sulfur with poly(vinyl chloride) is studied in 1,2,4-trichlorobenzene and without any solvent under various conditions. Black polymers containing 3.77–57.64% chemically bonded sulfur and, according to IR spectroscopy, including >C=C< and >C=S groups in macromolecules are obtained. It is shown that the diffraction curves of poly(vinyl chloride) and of the reaction product containing 7.82% almost coincide but that the thermal stability of the latter is considerably higher than that of the initial polymer. The prospects of the practical use of the products of the reaction of poly(vinyl chloride) with elemental sulfur are demonstrated.     

Synthesis, crystal structure and electrochemical properties of bis(ethylenedioxy)tetraselenafulvalene (BEDO-TSeF)

Bis(ethylenedioxy)tetraselenafulvalene (BEDO-TSeF) has been synthesized using elemental selenium as the only source of the selenium atoms, and its crystal structure and electrochemical properties are examined and compared with its sulfur analogues.     

Pentasulfide S5(2-) as the first tridentate chelating ligand in Ru(P(OE)3)3S5(E = Me and Et)

Room temperature stirring of H2Ru(P(OE)3)4 (E = Me and Et) and elemental sulfur in benzene afforded the optically active compounds Ru(P(OMe)3)3S5 (1) and Ru(P(OEt)3)3S5 (2). Compounds 1 and 2 are crystallized in the trigonal space group P31 with a = 14.231(10) A, c = 10.24(1) A, V = 1794(2) A3, and Z = 3, and orthorhombic space group P212121 with a = 15.393(5) A, b = 18.126(6) A, c = 12.421(4) A, V = 3465(1) A3, and Z = 4, respectively. Solutions of 1 and 2 did not show any optical activity since the bulk materials are racemic mixtures. The X-ray analyses also reveal that in both compounds polysulfide S5(2-) ion acts as a novel tridentate ligand, resulting in an asymmetric bicyclic RuS5 unit having three- and five-membered rings around the ruthenium atom. Fragmentation of the S5(2-) ring to S2- ion was observed in the presence of sulfur-abstracting reagents such as PR3 (R = Ph, OMe, and OEt) and also to S2(2-) ion when the compounds were reacted with RuCl2(P(OE)3)4 (E = Me and Et).     

Die Bildung von Gallium-Chalkogen-Heterokubanstrukturen durch Umsetzung der Alkylgallium(I)-Verbindung Ga4[C(SiMe3)3]4 mit Schwefel,Selen und Tellur

The Formation of Gallium Chalcogen Heterocubanes by the Reaction of the Alkylgallium(I) Compound Ga₄[C(SiMe₃)₃]₄ with Sulfur, Selenium, and Tellurium The alkylgallium(I) compound Ga₄[C(SiMe₃)₃]₄ 1 , which monomerizes in dilute solutions, reacts with elemental sulfur, selenium, and tellurium in boiling n-hexane to yield the corresponding Ga₄X₄R₄ cage compounds in a high yield. As shown by crystal structure determinations, the products have distorted Ga₄X₄ heterocubanes in their molecular centers with a slightly increasing distortion for the heavier chalcogen atoms. While the selenium and tellurium derivatives show a very low solubility in benzene, the sulfur compound dissolves readily accompanied by the dissociation into the (RGaS)₂ dimer.     

RE(Et2dtc)3(phen)(RE=La，Pr，Nd，Sm)的恒容燃烧能测定(英)

Four ternary solid complexes were synthesized with sodium diethyldithiocarbamate (NaEt₂dtc)(b), 1,10-phenanthroline (o-phen) (c) and hydrated lanthanide chlorides in absolute ethanol by an improved reported method. The complexes were identified as the general formula of RE(Et₂dtc)₃(phen) (RE=La, Pr, Nd, Sm) by chemical and elemental analyses. IR spectra of the complexes showed that the RE³⁺ was coordinated with sulfur atoms of NaEt₂dtc and nitrogen atoms of o-phen. The constant-volume combustion energies of complexes, Δ_cU, were determined by a precise rotating-bomb calorimeter at 298.15 K. The standard enthalpies of combustion, Δ_cH_m^?, and standard enthalpies of formation, Δ_fH_m^?, were calculated for these complexes, respectively.     

Synthesis of covellite (CuS) from the elements

A one-step, corrosion-assisted reaction was developed to synthesize copper sulfide (CuS) from elemental copper and sulfur in water at 60 °C. The as-prepared polycrystalline CuS consists of polyhedral-shaped 2–3 μm crystallites. CuS forms by the oxidation of copper metal in the presence of sulfur, whereas in the presence of water, a continuous solid-state reaction occurs without passivation by the product.     

Synthesis and structures of [[HC(CMeNAr)(2)]Ge(S)X] (Ar = 2,6-iPr(2)C(6)H(3), X = F,Cl, Me): structurally characterized examples with a formal double bond between group 14 and 16 elements bearing a halide

Treatment of [{HC(CMeNAr)2}GeX] (Ar = 2,6-iPr2C6H3, X = Cl (1), F (2)), with elemental sulfur at room temperature smoothly afforded the [{HC(CMeNAr)2}Ge(S)X] (X = Cl (3), F (4)). Compound 4 can also be obtained from 3 with the fluorination reagent Me3SnF. Reaction of 3 with MeLi led to the formation of [{HC(CMeNAr)2}Ge(S)Me] (5). Single-crystal X-ray structural analyses indicate compounds 3-5 are monomeric. The germanium centers adopt four coordinated sites and reside in distorted tetrahedral environment. Compounds 3 and 4 are structurally characterized examples with a formal double bond between group 14 and 16 elements bearing a halide.     

Molybdenum-catalyzed episulfidation of (E)-cycloalkenes with elemental sulfur

Episulfidation of (E)-cyclooctene and (E)-cyclononene was achieved with elemental sulfur by using a catalytic amount of a molybdenum oxo complex.     

Synthesis and Characterization of New N-(Diphenylphosphino)-Naphthylamine Chalcogenides: X-Ray Structures of (1-NHC10H7)P(Se)Ph2 and Ph2P(S)OP(S)Ph2

Abstract

The reaction of 1-naphthylamine with one equivalent of chlorodiphenylphosphine in the presence of triethylamine gave the (1-NHC₁₀H₇)PPh₂ (1) ligand. Refluxing of 1 with elemental sulfur or grey selenium in toluene (1:1 molar ratio) afforded (1-NHC₁₀H₇)P(S)Ph₂ (2) and (1-NHC₁₀H₇)P(Se)Ph₂ (3), respectively. Moreover, the byproduct {Ph₂P(S)}₂O (4) was isolated from the reaction of 1 with elemental sulfur. Compounds 1–3 were identified and characterized by multinuclear (¹H, ¹³C, ³¹P, ⁷⁷Se) NMR spectroscopy, mass spectrometry, and elemental analysis. Crystal structure determinations of 3 and 4 were carried out.     

Nickel-manganese sulfido carbonyl cluster complexes. synthesis, structure, and properties of the unusual paramagnetic complexes Cp2Ni2Mn(CO)3(mu 3-E)2, E = S, Se

The reaction of Mn(2)(CO)(7)(mu-S(2)) with [CpNi(CO)](2) yielded the paramagnetic new compound Cp(2)Ni(2)Mn(CO)(3)(mu(3)-S)(2) (1) and a new hexanuclear metal product Cp(2)Ni(2)Mn(4)(CO)(14)(mu(6)-S(2))(mu(3)-S)(2) (2). Structurally, compound 1 contains two triply bridging sulfido ligands on opposite sides of an open Ni(2)Mn triangular cluster. EPR and temperature-dependent magnetic susceptibility measurements of 1 show that it contains one unpaired electron. The electronic structure of 1 was determined by Fenske-Hall molecular orbital calculations which show that the unpaired electron occupies a low lying antibonding orbital delocalized unequally across the three metal atoms. The selenium homologue Cp(2)Ni(2)Mn(CO)(3)(mu(3)-Se)(2) (3) was obtained from the reaction of a mixture of Mn(2)(CO)(10) and [CpNi(CO)](2) with elemental selenium and Me(3)NO.2H(2)O. It also has one unpaired electron. Compound 1 reacted with elemental sulfur to yield the dinickeldimanganese compound, Cp(2)Ni(2)Mn(2)(CO)(6)(mu(4)-S(2))(mu(4)-S(5)), 4, which can also be made from the reaction of Mn(2)(CO)(7)(mu-S(2)) with [CpNi(CO)](2) and sulfur. Compound 4 was converted back to 1 by sulfur abstraction using PPh(3). The reaction of Mn(2)(CO)(10) with [CpNi(CO)](2) in the presence of thiirane yielded the ethanedithiolato compound CpNiMn(CO)(3)(mu-SCH(2)CH(2)S) (5), which was also obtained from the reaction of Mn(4)(CO)(15)(mu(3)-S(2))(mu(4)-S(2)) with [CpNi(CO)](2) in the presence of thiirane. Compound 5 reacted with additional quantities of thiirane to yield the new compound CpNiMn(CO)(3)[mu-S(CH(2)CH(2)S)(2)], 6, which contains a 3-thiapentanedithiolato ligand that bridges the two metal atoms. Compound 6 was also obtained from the reaction of Mn(2)(CO)(10) with [CpNi(CO)](2) and thiirane. The molecular structures of the new compounds 1-6 were established by single-crystal X-ray diffraction analyses.     

过渡金属氧化物催化剂上NH3 分解Claus反应机理研究

运用浸渍法制备了七种过渡金属氧化物催化剂.对于NH3 分解反应均可获得很高的NH3转化率;对于NH3分解Claus反应则可以获得较高的SO2转化率和单质硫选择性.通过比较发现Co3O4-TiO2和Fe2O3-TiO2催化剂的低温活性比较高.经过XRD表征发现,在NH3分解Claus反应中,催化剂的活性相可能是过渡金属硫化物.结合活性评价和XRD表征结果提出了NH3分解Claus反应的机理.     

Density functional theory study of the d(10) series (H3P)3M(eta 1-SO2) and (MenPh(3-n)P)3M(eta 1-SO2) (M = Ni, Pd, Pt; n = 0-3): SO2 pyramidality and M-S bond dissociation energies

Quantum mechanical density functional theory (DFT) and coupled DFT/molecular mechanics (QMMM) studies of the compounds (H(3)P)(3)M(eta(1)-SO(2)) and (Me(n)Ph(3-n)P)(3)M(eta(1)-SO(2)) (M = Ni, Pd, Pt; n = 0-3) model the experimental data well, particularly the planar/pyramidal geometries at sulfur. Bond dissociation energy (BDE) calculations confirm that Pd/Pt systems with pyramidal SO(2) ligands exhibit M-S BDEs smaller by 30-50% than Ni systems with planar SO(2). However, scans of the potential energy surfaces show that flexing the planar/pyramidal torsion angle within ranges of 20-30 degrees requires little energy. Bond energy decomposition calculations indicate that the electrostatic Delta E(elstat) term determines the BDE for Pd/Pt molecules where the sulfur is pyramidal, whereas all three terms matter when the sulfur is planar, as for Ni compounds. However, this accounts only for a fraction of the BDE differences; orbital energy matching accounts for the balance.     

Photoinduced reaction of sulfur with cyclopentadienyliron dicarbonyl dimer and crystal structure of bis(cyclopentadienyliron)monocarbonyl tetrasulfide

The photolysis of (π⁵-C₅H₄RFe(CO)₂)₂ with R = H or CH₃, in the presence of elemental sulfur, produces a mixture of organometallic tetrasulfides containing four sulfur and two iron atoms. The structure of one of such compounds has been determined by X-ray diffraction. It contains a core of four sulfur atoms between two irons. One iron is symmetrically linked to four sulfur atoms and to the cyclopentadienyl ring; the other iron is linked to only two sulfur atoms, one carbonyl, and a cyclopentadienyl group.     

Study of corrosion on copper strips by petroleum naphtha in the ASTM D-130 test by means of electronic microscopy (SEM) and energy dispersive X-ray (EDX)

Summary Corrosion in heat-engines has been attributed to some undesirable sulfur compounds present in petroleum naphthas, fuel-oils or gasolines. The corrosivity of these petroleum products is measured by means of the ASTM D-130 copper strip test, which is based on discoloration of a standard copper strip immersed into the petroleum products at 50°C for 3 h. The present paper studies various aspects of corrosivity of different sulfur compounds in petroleum naphthas by means of the ASTM D-130 test together with the electronic microscopy (SEM) and energy dispersive X-ray (EDX) techniques. These non-destructive techniques allow to know the strip corrosive morphology and to determine the sulfur concentration on this strip. Of the various types of sulfur compounds present in petroleum naphthas, the data show that elemental sulfur is corrosive to copper, but its corrosive level differes from naphtha to naphtha. Among the different mercaptans only ethyl-mercaptan presents corrosivity. The disulfides and sulfides tested are non-corrosive to copper.     

Extending the coordination chemistry of molecular P(4)S(3): the polymeric Ag(P(4)S(3))(+) and Ag(P(4)S(3))(2)(+) cations

Upon reacting P(4)S(3) with AgAl(hfip)(4) and AgAl(pftb)(4) [hfip = OC(H)(CF(3))(2); pftb = OC(CF(3))(3)], the compounds Ag(P(4)S(3))Al(hfip)(4) 1 and Ag(P(4)S(3))(2)(+)[Al(pftb)(4)](-) 2 formed in CS(2) (1) or CS(2)/CH(2)Cl(2) (2) solution. Compounds 1 and 2 were characterized by single-crystal X-ray structure determinations, Raman and solution NMR spectroscopy, and elemental analyses. One-dimensional chains of [Ag(P(4)S(3))(x)](infinity) (x = 1, 1; x = 2, 2) formed in the solid state with P(4)S(3) ligands that bridge through a 1,3-P,S, a 2,4-P,S, or a 3,4-P,P eta(1) coordination to the silver ions. Compound 2 with the least basic anion contains the first homoleptic metal(P(4)S(3)) complex. Compounds 1 and 2 also include the long sought sulfur coordination of P(4)S(3). Raman spectra of 1 and 2 were assigned on the basis of DFT calculations of related species. The influence of the silver coordination on the geometry of the P(4)S(3) cage is discussed, additionally aided by DFT calculations. Consequences for the frequently observed degradation of the cage are suggested. An experimental silver ion affinity scale based on the solid-state structures of several weak Lewis acid base adducts of type (L)AgAl(hfip)(4) is given. The affinity of the ligand L to the silver ion increases according to P(4) < CH(2)Cl(2) < P(4)S(3) < S(8) < 1,2-C(2)H(4)Cl(2) < toluene.     

Reaction of (carbonylimido)sulfur(IV) derivatives with TAS-fluoride, (Me2N)3S+Me3SiF2-

In the reaction of TAS-fluoride, (Me2N)3S+Me3SiF2-, with carbonyl sulfur difluoride imides RC(O)NSF2 (R = F, CF3), C-N bond, cleavage is observed, and TAS+RC(O)F2- and NSF are the final products. From TASF and RC(O)NS(CF3)F, the salts TAS+RC(O)NS(CF3)F2- (R = F (14), CF3 (15)), with psi-pentacoordinate sulfur centers in the anions, are formed. An X-ray structure investigation of 14 shows that the fluorine atoms occupy axial positions and CF3, NC(O)F, and the sulfur lone pair occupy equatorial positions of the trigonal bipyramid. The -C(O)F group lies in the equatorial plane with the CO bond synperiplanar to the SN bond. According to B3LYP calculations, this structure corresponds to a global minimum and the expected axial orientation of the -C(O)F group represents a transition state. Calculations for the unstable FC(O)NSF3- anion show a different geometry. The -C(O)F group deviates 40 degrees from axial orientation, and the equatorially bonded fluorine is, in contrast to the -CF3 group in 14, syn positioned.