Dimethyl- and Diethyltin(IV) Compounds with Perfluorobiphenyl-4-Thiolate and Perfluoronaphthalene-2-Thiolate Anions: The Crystal Structure of (CH3)2Sn(C12F9S)2

Compounds (CH₃)₂Sn(C₁₂F₉S)₂ (I), (CH₃)₂Sn(C₁₀F₇S)₂ (II), and (C₂H₅)₂Sn(C₁₀F₇S)₂ (III) were synthesized. Single crystals of Iwere grown and structurally characterized using X-ray diffraction analysis (1590 reflections, R = 0.0209). The crystals are orthorhombic, a = 40.848(8) Å, b = 6.058(1) Å, c = 11.183(2) Å, V = 2767(1) ų, (calcd.) = 2.024 g/cm³, space group Pbcn, Z = 4. The structure is built from monomeric molecules. The coordination polyhedron of the Sn atom (the SnC₂S₂ core) is a distorted tetrahedron. Compounds I–III are volatile when heated in vacuo. Thermolysis of these compounds results in SnO₂ (in air) or SnS₂ (in argon).     

Oxidation of methanol on Pt(Mo) electrodes obtained using galvanic displacement method

The electrocatalytic Pt-Mo system was obtained by formation of platinum particles on the Mo surface under its contact with PtC₆²⁻ (PtCl₄²⁻) under the open circuit conditions. Cyclic voltammograms of the obtained Pt(Mo) electrodes feature well pronounced peaks of hydrogen adsorption and desorption on Pt particles. Nonuniform platinum distribution across the electrode surface was found. Pt(Mo) electrodes showed a higher specific activity in the reaction of methanol oxidation in the potential range of 0.35–0.45 V (RHE) as compared to Pt/Pt.     

Formaldehyde interaction with adsorbed oxygen on open-circuit platinum electrodes in aqueous sulfuric acid solutions

The open circuit potential transients and cathodic potentiodynamic pulses were measured upon formaldehyde (methylene glycol) interaction with pre-adsorbed oxygen (O_ads) on Pt/Pt and pc Pt electrodes in aqueous sulfuric acid solutions. The slowest interaction of CH₂(OH)₂ with O_ads was observed in the high coverage range of the electrode surface (θ_O ～ 0.2 0.8 to 1). The process rate in this range is determined by the direct reaction of O_ads with CH₂(OH)₂ molecules from the bulk solution. In the middle surface oxygen coverage range (θ_O 0.2 to 0.8), CH₂(OH)₂ interaction with O_ads takes place by the mechanism of “conjugated reactions”. The kinetic parameters of reactions for CH₂(OH)₂, HCOOH, and CH₃ OH were compared. The rate of CH₂(OH)₂-O_ads interaction on Pt electrodes in the high oxygen coverage range was found higher by an order of magnitude than that of HCOOH and by two orders of magnitude than in the case of CH₃OH.     

95Mo and 17O NMR studies of aqueous molybdate solutions

Aqueous molybdate solutions with molybdenum concentrations of [Mo]=1, 0.4, and 0.2 M have been studied by NMR at pH 7-1 and in 0.3-6 M HClO4. The 95Mo NMR spectrum of isopolyanion (IPA) Mo7O24(6-) (I) at pH=5 consists of a signal at 210 ppm and two overlapping peaks at 32 and approximately 15 ppm with the intensity ratio approximately 1:4:2, and that of beta-Mo8O26(4-) (II) consists of two signals at approximately 100 and 10 ppm with the intensity ratio approximately 1:3. A broad 95Mo NMR line at around 0 ppm was observed in the pH range of IPA Mo36O112(8-) (III), and a signal of cationic oxospecies including MoO2(2+) (IV) was observed from -62 to -69 ppm. Two protonation sites of IPA I have been identified from 17O NMR spectra, which suggests binding of up to two protons. The distribution diagram, derived from the 95Mo NMR spectra, is given for [Mo]=0.4 M. The 95Mo NMR signals shift to lower frequencies with increasing number and strength of the Mo-O terminal bonds.     

Substituted 1,3,2,4‐benzodithiadiazines and related compounds

Despite some limitations, the 1:1 condensation of n‐RC₆H₄‐N=S=N‐SiMe₃ (n = 2, 3, 4; R = CH₃, OCH₃, F, Cl, CF₃) with SCl₂, followed by intramolecular electrophilic ortho‐cyclization, was found to be a general synthetic approach to the corresponding 5‐R, 6‐R, and 7‐R–substituted 1,3,2,4‐benzodithiadiazines, formally antiaromatic 12π‐electron compounds. For precursors with n = 3, the high regioselectivity of the cyclization resulted in exclusive (R = OCH₃, F) or predominant (R = CH₃, Cl) formation of 6‐R isomers; the ratio of the major 6‐R isomer to the minor 8‐R one was found to be 72:28 (R = CH₃) or 78:22 (R = Cl). The preferred direction of cyclization is consistent with thermodynamics of the corresponding intermediate σ‐complexes as well as factors of kinetic control for an orbital‐controlled El‐Nu reaction. According to the X‐ray diffraction data, the molecules of 5‐CF₃ (15) and 6‐F (12) derivatives are nearly planar, while the molecules of 5‐OCH₃ (7) and 6‐CH₃ (4) derivatives are bent along the S¹ … N⁴ line by ∼11° (7) or 7° (4). An attempt to adopt CsF‐induced intramolecular nucleophilic ortho‐cyclization of Ar_F‐S‐N=S=N‐SiMe₃ into polyfluorinated 1,3,2,4‐benzodithiadiazines for polyfluoropyridine derivatives resulted in formation of polyfluorinated aminopyridines. Data obtained are consistent with a previously suggested scheme of sulfur–nitrogen chain shortening during cyclization. Mild acid hydrolysis of the title compounds was shown to be a convenient synthetic route to substituted 2,2′‐diaminodiphenyl disulfides (including polyfluorinated ones) via the corresponding 2‐aminobenzenethiols. © 1999 John Wiley & Sons, Inc. Heteroatom Chem 10: 113–124, 1999     

Mössbauer study of thermal decomposition of the [FeCp(SPh)CO]2 complex and its reaction with the surface of activated silica gel

Thermal decomposition of the [FeCp(SPh)CO]₂ complex and its reaction with the surface of activated silica gel were investigated by Mössbauer spectroscopy. A small amount of a complex with properties similar to ferrocene is separated in the first stage of thermal decomposition (120–130°C). The starting carbonyl complex totally disappears in the second stage (165–210°C), and two compounds are present among the products: a derivative of ferrocene and the final product, an x-ray amorphous, iron-containing structure with an ionic-covalent type of chemical bond (CB) and a 25 and 5 wt. % concentration of oxygen and sulfur, respectively. The Mössbauer parameters of this product and the compound formed in the reaction of [FeCp(SPh)CO]₂ with the surface of activated silica gel at 4.2–300 K are identical. The analysis of the data suggested that both structures are highly disperse clusters of iron oxide with the structure of an inverted spinel with superparamagnetic properties.Deceased.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 771–778, April, 1991.We would like to thank Yu. B. Kopylovskii for assistance in processing the spectra with the MESLIN program.     

Electrochemical oxidation of dyes on oxide lead anode with the involvement of active oxygen species

Kinetics and selectivity of oxidation of dyes (Methyl Orange and Chrome Dark Blue) on a lead dioxide (Pb/PbO₂) anode at various current densities, substrate concentrations, and pH values with the use of various active oxygen species was studied. It was shown that the electrochemical oxidation of dyes on the Pb/PbO₂ anode occurs rather effectively under the chosen conditions. The mineralization efficiency in 5 h was 51 to 89.5 and 93 to 100% for, respectively, Methyl Orange and Chrome Dark Blue, depending on the electrolysis conditions.     

Generation of a Hetero Spin Complex from Iron(II) Iodide with Redox Active Acenaphthene-1,2-Diimine

The reaction of the redox active 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (dpp-BIAN) and iron(II) iodide in acetonitrile led to a new complex [(dpp-BIAN)Fe^III₂] (1). Molecular structure of 1 was determined by the single crystal X-ray diffraction analysis. The spin state of the iron cation in complex 1 at room temperature and the magnetic behavior of 1 in the temperature range of 2–300 K were studied using Mossbauer spectroscopy and magnetic susceptibility measurements, respectively. The neutral character of dpp-BIAN in 1 was confirmed by IR and UV spectroscopy. The electrochemistry of 1 was studied in solution and solid state using cyclic voltammetry. The generation of the radical anion form of the dpp-BIAN ligand upon reduction of 1 in a CH₂Cl₂ solution was monitored by EPR spectroscopy.