Reaction of thiophenol with vinyl ethees in the presence of iron pentacarbonyl

Conclusions Iron pentacarbonyl is an inhibitor for the free-radical addition of thiophenol to vinyl ethers and the cis-trans isomerization of unsaturated compounds, initiated by thiyl radicals.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2250–2253, October, 1972.     

Telomerization of aceylonitkile and methyl acrylate with bromotrichloromethane in the presence of iron pentacarbonyl

Conclusions Initiating systems that contain iron pentacarbonyl and a cocatalyst (iodine, dimethylaniline) make it possible to run the telomerization of acrylonitrile and methyl acrylate with bromotrichloromethane under mild conditions, with a total yield of 55–65% of the first two telomer homologs.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 181–184, January, 1973.     

Ionic liquids in Barbier-Zaitsev reaction. Synthesis of 1-(perfluorophenyl)-2-phenylethanol in the presence of iron pentacarbonyl

The addition of benzyl bromide to pentafluorobenzaldehyde promoted by metal complex systems underlain by Fe(CO)₅ in the presence of a molar amount of ionic liquid led to the formation of 1-(perfluorophenyl)-2-phenylethanol in up to 60% yield.     

Telomerization of ethylene with 1,1,1,3-tetrachloropropane in the presence of iron pentacarbonyl and isopropyl alcohol

Conclusions Polychlorinated hydrocarbons containing the CCl₃ group can be used as telogens in the telomerization of olefins in the presence of iron pentacarbonyl and i-C₃H₇OH. The formation of the telomer homologs in high yield obeys the general rules that were established for the given initiating system.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2837–2839, December, 1971.     

Voltammetric study of the interaction of pentoxifylline (PTX) with Zn(II) in the presence and absence of cysteine

The interaction of pentoxifylline (PTX) with Zn(II) in the presence and absence of cysteine at physiological pH (7.40) was investigated for the first time by square-wave and cyclic voltammetry techniques. The Zn(II)–PTX complex was found to be an electroinactive inert complex, the composition of the formed complex is 1?:?1 (metal?:?ligand), and the logarithm of its stability constant (log β_1?:?1) was determined as 3.46 by direct monitoring of the current of free zinc(II). The logarithm of the stability constant (log β_1?:?2) and stoichiometry of the complexation of Zn(II) with cysteine were determined to be 9.94 and 1?:?2, respectively. The stability constants were in agreement with those calculated from electronic spectral data. In the presence of cysteine, Zn(II)–PTX dissociated and an irreversible peak for Zn(II)–cysteine appeared at ?1.342?V. Cysteine prevents complex formation of Zn(II) with PTX.     

Kinetics of the light-driven aqueous autoxidation of sulfur(IV) in the absence and presence of iron(II)

The photochemical autoxidation of aqueous, acidic sulfur(IV) solutions was studied in the absence and presence of iron(II) by a newly introduced technique using a diode-array spectrophotometer, in which the same light source is used to drive and detect the reaction. Based on detailed kinetic and stoichiometric data sets, a non-chain mechanism is proposed for the autoxidation of sulfur(IV). In this mechanism, excited hydrated sulfur dioxide, *H2O.SO2, first reacts with O2 to form peroxomonosulfate ion, HSO5-, which rapidly oxidizes another H2O.SO2 to give hydrogensulfate ion as a final product. In the presence of iron(II), the formation of iron(III) was detected, which can be interpreted through the simultaneous contribution of two additional pathways: some of the HSO5- formed oxidizes iron(II) instead of sulfur(iv), and *H2O.SO2 also reacts directly with iron(II) to yield iron(III). This mechanism provides a sufficient quantitative interpretation of all experimental observations.     

[Fe(CO)2P(OPh)32(CS)]. The first stable thiocarbonyl derivative of iron(0) pentacarbonyl

In some circumstances, P-nBu₃ pr P-nBu₃/CC1₄ desulphurises [Fe(CO)₂{P(OPh)₃}₂(CS₂)] to give [Fe(CO)₂{P(OPh)₃}₂(CS)] which has trigonal bipyramidal coordination about the iron atom with the phosphite ligands in axial positions.     

Oxidation of furfural with H2O2 in the presence of a photogenerated iron catalyst

Visible irradiation of a methanolic solution of furfural containing dilute aqueous H₂O₂ and [FeCp(C₆H₅R)]PF₆ (1: R  H, Cl or CH₃) as catalyst yields methyl 2-furoate quantitatively. After photodecomplexation, the inorganic Fe^II,III catalyst can be isolated and recycled several times with unchanged activity in dark reactions at 20°C.     

Complexes of rhodium(III) and iridium(III) with the mono-oximes of 1,2-naphthoquinone: X-ray crystal structure of pyridinium trichloro(1,2-naphthoquinone 1-oximato)(pyridine)iridate(III)

The complexes M(1-nqo)₃ (M = Rh or Ir, 1-nqoH = 1,2-naphthoquinone 1-oxime) and M(2-nqo)₃ (M = Rh or Ir, 2-nqoH = 1,2-naphthoquinone 2-oxime) were prepared by the interaction of the quinone oxime with hydrated rhodium(III) chloride or chloroiridic(III) acid. The mixture resulting from the reaction of chloroiridic(III) acid and 1,2-naphthoquinone 1-oxime on treatment with pyridine afforded [pyH][Ir(1-nqo) (py)Cl₃] which was characterized by X-ray crystallography. The complexes Rh(1-nqo)₃ and Rh(2-nqo)₃ were also obtained by the nitrosation of the respective naphthol in the presence of hydrated rhodium(III) chloride. None of the trischelates showed any tendency to react with pyridine, triphenylphosphine or aqueous hydrochloric acid.     

The nature of the product from the reaction of tetracyanoethylene with iron pentacarbonyl

The reaction of tetracyanoethylene with iron pentacarbonyl in mesitylene at 90° gave an insoluble product, Fe₂C₁₆H₁₂N₈O₇. The Mössbauer and IR spectra, the magnetic susceptibilities over the temperature range 95–298 K, and the thermal decomposition temperatures in a nitrogen atmosphere were measured. The solid is best described as an iron (III) ketoamine polymer with hydroxo bridges between iron atoms.     

Synthesis and structure of the 1,2-isopropylidene-α-D-glucofuranose 3,5,6-bis-cyclophosphite complex with tungsten(0) pentacarbonyl

Metallocomplexes with optically active ligands are of considerable interest as catalysts of stereoselective processes. A complex of 1,2-isopropylidene-α-D-glucofuranose 3,5,6-bis-cyclophosphite with tungsten(0) pentacarbonyl has been synthesized for the first time and studied by X-ray crystallography.     

The interaction of H(2)O(2) with ice surfaces between 203 and 233 K

The interaction of H(2)O(2) with ice surfaces at temperatures between 203 and 233 K was investigated using a low pressure, coated-wall flow tube equipped with a chemical ionisation/electron impact mass spectrometer. Equilibrium surface coverages of H(2)O(2) on ice were measured at various concentrations and temperatures to derive Langmuir-type adsorption isotherms. H(2)O(2) was found to be strongly partitioned to the ice surface at low temperatures, with a partition coefficient, K(linC), equal to 2.1 × 10(-5) exp(3800/T) cm. At 228 K, this expression results in values of K(linC) which are orders of magnitude larger than the single previous determination and suggests that H(2)O(2) may be significantly partitioned to the ice phase in cirrus clouds. The partition coefficient for H(2)O(2) was compared to several other trace gases which hydrogen-bond to ice surfaces and a good correlation with the free energy of condensation found. For this class of trace gas a simple parameterisation for calculating K(linC)(T) from thermodynamic properties was established.